JPH1045945A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which does not cause the corrosion of a nozzle or a mold when molded and has excellent light resistance and stable quality by mixing a halogen-free thermoplastic resin with an aryl-containing phosphoric ester flame retardant and specifying the contents of chlorine and bromine and the content of a phenol. SOLUTION: This composition contains 65-99 pts.wt. thermoplastic resin (A) which contains no halogen in the molecular structure and 35-1 pt.wt. aryl- containing phosphoric ester flame retardant (B) (A+B=100 pts.wt.). The total content of chlorine and bromine should be 2wt.ppm or below based on the total of components A and B, and the content of a phenol should be 0.1wt.% or below. Component B is desirably a triaryl phosphate or an aryl phosphoric ester oligomer produced by the dehydrochlorination reaction of phosphorus oxychloride with a phenol or a phosphoric ester mixture thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition flame-retarded with a phosphate ester. For more information,
The present invention relates to a non-halogen flame-retardant resin composition which does not cause corrosion of a nozzle or a mold during extrusion and molding and has excellent light resistance.

[0002]

2. Description of the Related Art Synthetic resins are generally light, excellent in water resistance, chemical resistance, electrical insulation and mechanical properties, and are easy to mold. Therefore, they are used for building materials, electrical equipment materials, automotive materials, and fiber materials. Widely used as such. However, the synthetic resin has a disadvantage that it is easily burned as compared with a metal material and an inorganic material. For this reason, a number of methods for flame retarding synthetic resins have been proposed, but the most commonly used method is to add a flame retardant such as an inorganic hydroxide, an organic halide, or a phosphoric ester.

Of these, organic halides, particularly bromides, have excellent flame retardancy and are most commonly used. However, this flame retardant causes a large amount of smoke in a fire, is corrosive, and generates a gas containing halogen which is harmful to the human body. Therefore, a non-halogen flame-retardant resin is desired. As the flame retardant containing no halogen element, inorganic hydroxides such as aluminum hydroxide and magnesium hydroxide are known. However, these have low flame-retardant performance, and in order to obtain a sufficient effect, it is necessary to add tens to hundreds of parts by weight based on 100 parts by weight of the resin. There is a problem that falls,
Applications are limited.

On the other hand, phosphoric esters, which are another typical compound of non-halogen flame retardants, exhibit excellent flame retardancy, especially for resins containing an oxygen atom in the molecule, and are particularly excellent in thermal stability. , A phosphate ester having an aryl group is
Widely used mainly in engineering plastics such as polycarbonate resin and modified polyphenylene ether resin.

[0005] Of the synthetic resins, thermoplastic resins are usually mixed with an extruder and a flame retardant, and molded using an injection molding machine or the like. However, when a phosphate ester flame retardant is used for a resin with a relatively high extrusion molding temperature, especially for engineering plastics, sometimes the nozzles and molds are corroded during extrusion and molding, or the light resistance of the resin product decreases. And so on.

[0006]

SUMMARY OF THE INVENTION The present invention relates to an extruder,
An object of the present invention is to provide a stable halogen-free flame-retardant resin composition which does not cause corrosion of a nozzle or a mold during molding and has excellent light resistance.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the main causes of corrosion of nozzles and molds and deterioration of light resistance are chlorine contained in the resin composition. And bromine and phenols, and completed the present invention. That is, the present invention is as follows. 1. (A) 65 to 99 parts by weight of a thermoplastic resin containing no halogen element in its molecular structure; And 100 parts by weight of the total of components (B)), and the total content of chlorine and bromine is 2 ppm by weight or less with respect to the total of components (A) and (B), and A flame-retardant resin composition having a phenol content of 0.1% by weight or less. 2. (A) the thermoplastic resin is a polystyrene resin, a polycarbonate resin, a polyphenylene ether resin,
2. The flame-retardant resin composition according to the above item 1, which is a polyamide resin, a polyester resin, a thermoplastic elastomer, or a mixture thereof. 3. (B) The flame retardancy according to the above (1), wherein the phosphate ester flame retardant is a triaryl phosphate, an aryl phosphate oligomer, or a phosphate mixture containing these produced by a dehydrochlorination reaction between phosphorus oxychloride and phenols. Resin composition.

Hereinafter, the present invention will be described in detail. Examples of the thermoplastic resin which does not contain a halogen element in the molecular structure, which is the component (A) of the present invention, include polystyrene resins such as polystyrene, impact-resistant polystyrene, AS resin and ABS resin, dihydric phenol, and phosgene. A polycarbonate resin obtained by a reaction with a carbonate precursor such as or a transesterification reaction with a carbonate precursor such as diphenyl carbonate, a polyphenylene ether resin such as 2,6-diphenyl polyphenylene ether,
Polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as high density polyethylene, low density polyethylene and polypropylene Resin, polyester, polyether, adipate,
Examples thereof include thermoplastic polyurethanes such as lactones, styrene-butadiene block copolymers, thermoplastic elastomers such as ethylene-propylene elastomers and ethylene ionomers, polysulfone resins, polyethersulfone resins, and combinations thereof. In particular, one selected from a polystyrene resin, a polycarbonate resin, a polyphenylene ether resin, a polyamide resin, a polyester resin, and a thermoplastic elastomer.
Thermoplastic resin composed of a kind or a combination of two or more kinds has a remarkable flame retardant effect by a phosphate ester flame retardant,
It is preferably used.

The phosphoric ester flame retardant having an aryl group, which is the component (B) of the present invention, is a compound represented by the following general formula and a mixture thereof.

[0010]

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(In the formula, at least one of R1 to R4 is an aryl group and the others are each independently an alkyl group or an aryl group. A is a divalent phenol residue or a divalent or higher alcohol residue. And n is an integer of 0 to 10.) Examples of the aryl group represented by R1 to R4 in the formula include phenyl, tolyl, xylyl, trimethylphenyl, propylphenyl, and butylphenyl. Group, nonylphenyl group, hydroxyphenyl group, biphenyl group,
Examples include a naphthyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group,
A decyl group and the like can be mentioned. Examples of the divalent phenol residue represented by A in the formula include residues such as hydroquinone, resorcinol, biphenol, bisphenol A, and bisphenol S;
Examples of the dihydric alcohol residue include residues such as ethylene glycol, propylene glycol, butanediol, and pentaerythritol.

In the above formula, n is 0, R1,
Triaryl phosphates in which R2 and R4 are aryl groups and arylphosphate ester oligomers in which n is 1 or more, all of R1 to R4 are aryl groups, and A is a divalent phenol residue are excellent in flame retardancy. Particularly, the latter aryl phosphate ester oligomer is preferably used because it does not cause smoke or mold contamination during extrusion molding.

The mixing ratio of the thermoplastic resin (A) to the phosphate ester flame retardant (B) is such that the thermoplastic resin (65) is based on 100 parts by weight of the total of the components (A) and (B). To 99 parts by weight, and 35 to 1 part by weight of a phosphoric ester flame retardant.
The range of 5 parts by weight and the range of 25 to 5 parts by weight of the phosphoric ester flame retardant are preferred. When the addition amount of the phosphate ester flame retardant exceeds 35 parts by weight, physical properties such as heat resistance of the resin composition are significantly reduced, and when the addition amount of the flame retardant is less than 1 part by weight,
Sufficient flame retardant effect cannot be obtained.

According to the study of the present inventors, the main causes of mold corrosion during extrusion and molding and deterioration of the light resistance of the resin composition are chlorine, bromine and phenols contained in the resin composition. In particular, it has been found that the presence of chlorine, bromine or phenols exceeding a specific concentration in the resin composition causes a particularly serious problem. Therefore, the total content of chlorine and bromine is 2 ppm by weight or less based on the sum of the thermoplastic resin (A) and the flame retardant (B).
The content of phenols must be 0.1% by weight or less. The total content of chlorine and bromine is 1% by weight or less, and the content of phenols is preferably 0.03% by weight or less.

[0015] Phosphoric ester flame retardants are usually used in the presence of a catalyst.
Alternatively, it can be obtained by reacting a phosphorus halide such as phosphorus oxyhalide or phosphorus pentachloride with a phenol and, if necessary, an alcohol in the absence of a catalyst. Therefore, the phosphoric acid ester at the end of the synthesis is a composition containing a considerable amount of unreacted phenols and chlorine and bromine derived from raw materials, and the chlorine, bromine and phenol in the resin composition of the present invention. Most of the classes are usually derived from phosphate ester flame retardants.

Therefore, in a normal case, the total content of chlorine and bromine when the phosphate ester flame retardant is added to the thermoplastic resin is the sum of the thermoplastic resin (A) and the phosphate ester flame retardant (B). A phosphate ester flame retardant purified by a method such as distillation or washing is used so that the content of phenols is 2% by weight or less and the content of phenols is 0.1% by weight or less. In this way, nozzle and mold corrosion,
In addition, a resin composition having no problem of a decrease in weather resistance can be obtained. When chlorine, bromine or phenols are contained in the resin and other additives, the total content of chlorine and bromine, including these contents, is calculated as the thermoplastic resin (A) and the phosphate ester. 2 based on the sum of the flame retardants (B)
It must be below ppm by weight and phenols below 0.1% by weight.

The resin composition of the present invention may contain other non-halogen flame retardants, for example, inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid and ammonium phosphate, as long as the effects of the present invention are not impaired.
Melamine, urea, methylolmelamine, dicyandiamide, nitrogen-containing compounds such as melamine resin, urea resin, inorganic hydroxides such as aluminum hydroxide and magnesium hydroxide, antimony oxide, molybdenum oxide, ammonium molybdate, zinc oxide, zinc borate, An inorganic compound such as tin oxide, an anti-dripping agent such as polytetrafluoroethylene and a siloxane compound may be used in combination.

The resin composition of the present invention may contain other additives such as stabilizers such as ultraviolet absorbers and antioxidants, plasticizers, mold release agents, dyes and pigments as long as the effects of the invention are not impaired. And fillers such as glass fiber, glass chip, glass beads, carbon fiber, calcium carbonate, talc, mica, wood powder, slate powder, and fibrous asbestos.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. The chlorine content and the bromine content of the flame retardant and the resin composition used in the examples were determined by weighing about 0.1 g of a sample, burning it by a combustion tube combustion method, capturing generated halogen by water absorption, It was quantified by chromatography.
Phenols are obtained by dissolving a sample in 50 times the volume of tetrahydrofuran and performing high-performance liquid chromatography (column:
It was quantified by an absolute calibration curve method using Tosoh TSKgel ODS-80T, solvent: methanol / water = 90/10).

The resins, flame retardants and additives used in the examples are shown below. 1. Resin [A-1 polyphenylene ether resin] Poly 2,6-dimethyl-1,4-phenylene ether resin having an intrinsic viscosity of 0.52 measured at 30 ° C. in chloroform [A-2 polycarbonate resin] Teijin Chemicals Ltd. Panlite L1250 (trade name) [A-3 polystyrene resin] manufactured by Asahi Kasei Corporation
Asahi Kasei Polystyrene 685 (trade name) [A-4 Impact-resistant polystyrene resin] Asahi Kasei Kogyo Co., Ltd. Asahi Kasei Polystyrene 9405 (trade name) [A-5 ABS resin] Asahi Kasei Kogyo Co., Ltd. Styrac 6920 (rubber component 30) (% By weight) (product name) Flame retardant [B-1] triphenyl phosphate having a chlorine content of less than 0.1 ppm by weight and a phenol content of 0.1% by weight [B-2] a chlorine content of 1 ppm by weight, a phenol content of 0.2% by weight, a phosphoric ester oligomer represented by the following formula having a weight average value of 1.3:

[0021]

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[B-3] A chlorine content of 5 wt ppm, a cresol content of 0.4 wt%, and a weight average value of n of 1.5
A phosphate ester oligomer represented by the following formula:

[0023]

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[B-4] A chlorine content of 2 wt ppm, a phenol content of 1.8 wt%, and a weight average value of n of 1.3.
A phosphate ester oligomer represented by the following formula:

[0025]

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[B-5] A chlorine content of 32 weight ppm,
Phenol content 0.5% by weight, weight average value of n 1.3
A phosphate ester oligomer represented by the following formula:

[0027]

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3. Additive [Anti-drip agent] Polytetrafluoroethylene Daiflon F201L (trade name) manufactured by Daikin Industries, Ltd. [Light stabilizer] Tinuvin 622 manufactured by Ciba Geigy Co., Ltd.
LD (trade name) Next, a method for evaluating the resin composition will be described. 1. Light fastness: 150 using a xenon weather meter
After the light fast acceleration test for a long time, the color difference (ΔE) from that before the test was measured. 2. Mold Corrosion: After performing 5,000 shots molding with an injection molding machine, the mold was visually evaluated. 3. Flame retardancy: Measured based on the UL94 standard vertical combustion test using a 1/12 inch test piece.

[0029]

EXAMPLE 1 60 parts by weight of resin A-1, 10 parts by weight of A-3, 20 parts by weight of A-4, 10 parts by weight of flame retardant B-1 and 0.5 parts by weight of light stabilizer Blend at the ratio of
The mixture was kneaded with a twin-screw extruder in which the cylinder temperature was set at 300 ° C. to obtain resin composition pellets. The pellet was molded by an injection molding machine at a cylinder temperature of 300 ° C. to obtain a test piece. Table 1 shows the evaluation results.

[0030]

Examples 2 and 3 and Comparative Examples 1 and 2 B-
Except for using 10 parts by weight of B-2 to B-5 instead of 1, the resin composition was kneaded and molded under the same composition and conditions as in Example 1 to obtain each test piece. Table 1 shows the evaluation results.

[0031]

Example 4 60 parts by weight of resin A-2, 25 parts by weight of A-5, 15 parts by weight of flame retardant B-1 and 0.2 parts by weight of a dripping inhibitor were blended. 2
The mixture was kneaded by a twin-screw extruder set at 40 ° C. to obtain pellets of the resin composition. The pellets are heated at a cylinder temperature of 250.
A test piece was obtained by molding with an injection molding machine at ℃. Table 2 shows the evaluation results.

[0032]

Examples 5 and 6 and Comparative Examples 3 and 4 As flame retardants, B-
Except for using 15 parts by weight of B-2 to B-5 instead of 1, the resin composition was kneaded and molded under the same composition and conditions as in Example 4 to obtain each test piece. Table 2 shows the evaluation results.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

Industrial Applicability The flame-retardant resin composition of the present invention has excellent light resistance, does not corrode a nozzle or a mold at the time of extrusion and molding, and is extremely useful in industry.

Claims (3)

[Claims] 1. A composition comprising: (A) 65 to 99 parts by weight of a thermoplastic resin containing no halogen element in its molecular structure; and (B) 35 to 1 parts by weight of a phosphoric ester flame retardant having an aryl group. Represents 100 parts by weight of the total of the components (A) and (B)), and the total content of chlorine and bromine is 2 parts by weight based on the total of the components (A) and (B). p
pm or less and the content of phenols is 0.1% by weight
A flame-retardant resin composition comprising: 2. The method according to claim 1, wherein (A) the thermoplastic resin is a polystyrene resin, a polycarbonate resin, a polyphenylene ether resin, a polyamide resin, a polyester resin, a thermoplastic elastomer, or a mixture thereof. Flammable resin composition. 3. The phosphoric ester flame retardant (B) is a triaryl phosphate or aryl phosphate oligomer produced by a dehydrochlorination reaction between phosphorus oxychloride and phenols, or a phosphoric ester mixture containing these. 2. The flame-retardant resin composition according to 1.