JP2001011461A - Bromine-containing flame-retarded composition having resistance to iron oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retarded composition, which is able to prevent occurrence of defective molded articles ascribed to the reaction of a flame retardant with an iron oxide deposited on an apparatus by adding an epoxy compound, an organotin compound, a chelating agent or a mixture thereof to a bromine-containing flame retardant wherein both the flame retardant alone and its mixture with the iron oxide exhibit a specified heat loss characteristic. SOLUTION: The bromine-containing flame retardant, is such that the heat loss of a flame retardant alone is not larger than 0.1 wt.% under conditions of 130 deg.C×2 hours, and 1% and 5% heat loss temperatures, which are, respectively, measured according to differential thermal analysis (heat-up rate of 10 deg.C/minute), of a mixture of the flame retardant and iron oxide at a ratio by weight of 20:1 in a stream of air are, respectively, lower at least by 30 deg.C than the 1% and 5% heat loss temperatures measured according to the differential thermal analysis of the flame retardant alone under the same conditions. Such a bromine-containing flame retardant is mixed with an epoxy compound having an epoxy equivalent of 1,000 or below, an organotin compound, a chelating agent or a mixture thereof in an amount of 0.01 to 50 wt.% based on the flame retardant. These additives may be used singly or in combination.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a flame retardant composition having iron oxide resistance, and more particularly, to molding of a thermoplastic resin containing a flame retardant.
The iron oxide (F
The occurrence of defective molded articles due to the reaction with _{e 2 O 3, Fe 3 O} 4 , etc.) can be prevented, it relates to a flame retardant composition.

[0002]

BACKGROUND OF THE INVENTION It is well-known that plastic molded articles, including electric and electronic parts, which require flame retardancy, are made flame-retardant with a flame retardant and a flame retardant aid such as antimony trioxide. . The thermoplastic resin composition containing a bromine-based flame retardant used for this purpose suppresses the generation of decomposition products such as bromine radicals and hydrogen bromide generated by the thermal decomposition of the flame retardant at a temperature not lower than the melting temperature of the resin, or suppresses it. It generally contains catching heat stabilizers, thereby preventing resin coloration and equipment corrosion.

[0003] Apart from the problem caused by the thermal decomposition products of the flame retardant at temperatures above the melting temperature of the resin, depending on the flame retardant included if the extruder or other molding machine has been used for a long time, An unexpected molding defect may occur. The cause was not clarified so far, and when pursued, iron oxide was gradually deposited inside the device due to burns and rust, which came into contact with the brominated flame retardant and produced iron bromide. I understand. If the formed iron bromide remains on the mold surface, the molded product surface will be depressed and sink marks will appear, resulting in molding failure.If the iron bromide is incorporated into the molded product, it will absorb moisture during handling or during use after molding. Swelling,
This may cause defects such as voids. The solution of this problem is the subject of the present invention.

[0004]

The problems associated with the iron bromide formed by the reaction of the iron oxide and the flame retardant deposited inside the molding apparatus described above are not specific to all of the bromine-containing flame retardants, but to a specific group of flame retardants. Specifically or unacceptably practically. Therefore, a standard that can identify such a group is needed.

In the present invention, the target brominated flame retardant (a) is specified using the following criteria.

(1) In the heat loss test of the flame retardant alone at 130 ° C. × 2 hours, the heat loss is 0.1% by weight or less.

(2) Weight ratio of the flame retardant to iron oxide: 2
When the mixture of 0: 1 is measured by differential thermal analysis in a stream of air at a heating rate of 10 ° C./min, the 1% and 5% weight loss temperatures measured by differential thermal analysis under the same conditions using the flame retardant alone. Each corresponding weight loss temperature is at least 3
0 ° C lower.

An object of the present invention is to provide (a) a bromine-containing flame retardant satisfying the above criteria, and (b) 0.01 to 5 of the flame retardant.
The problem is solved by providing a flame retardant composition comprising 0% by weight of an epoxy compound having an epoxy equivalent of 1000 or less, an organotin compound, a chelating agent or a mixture thereof.

[0009]

Specific examples of brominated flame retardants meeting the above-mentioned criteria include tetrabromocyclooctane, hexabromocyclododecane (abbreviation HBCD), tribromophenyl-
Dibromopropyl ether, tribromophenyl-1,
2-dibromo-2-methylpropyl ether (abbreviation TB)
P-MDBPE), tetrabromobisphenol A-bisdibromopropyl ether (abbreviation: TBBA-BDBP)
E), tetrabromobisphenol S-bisdibromopropyl ether (abbreviation TBBS-BDBPE), trisdibromopropyl isocyanurate (abbreviation TDBPI)
C), but not limited thereto.

On the other hand, for example, tristribromoneopentyl phosphate (abbreviation TTBNPPP) and tristribromophenoxytriazine (abbreviation TTBPT)
A) does not satisfy the criterion (2) described above. Table 1 below shows 1% and 5% of the flame retardant alone and its iron oxide mixture.
The measured value of% weight loss temperature is shown.

[0011]

[Table 1]

The flame retardant composition of the present invention prevents the occurrence of defective molded products during the molding of the thermoplastic resin added due to the iron bromide generated by the reaction between the above flame retardant and iron oxide. As an inhibitor component, an epoxy equivalent of 100
It contains 0 or less epoxy compounds, organotin compounds, chelating agents or mixtures thereof. Examples of individual inhibitor components are set forth below, but are not limited thereto.

(B-1) Epoxy compound: α-olefin epoxide having 8 to 30 carbon atoms: 8 carbon atoms
It is obtained by oxidation of the above 1-alkene such as 1-octene or polybutadiene oligomer having a degree of polymerization of 2 or more.

Epoxidized unsaturated fatty acid triglyceride:
This includes epoxidized soybean oil, epoxidized linseed oil and the like.

Monoglycidyl ether: phenylglycidylether, o-phenylphenylglycidylether and the like.

Polyglyceryl ether of polyhydric phenol:
One example is known as a bisphenol-type epoxy resin. These are obtained by reacting epichlorohydrin with bisphenol A, bisphenol F, bisphenol S, and their bromides. As polyhydric phenols, novolak phenol resins, novolak cresol resins, novolak resins such as brominated novolak phenol resins, or polyglycidyl ethers obtained by starting from 4,4′-hydroxybiphenyl compounds and 1,
1,2,2-Tetrakis (p-2,3-epoxypropylphenyl) ethane is also included in this example.

Polyhydric alcohol polyglycidyl ether:
It is known as a polyglycidyl ether type epoxy resin of an aliphatic polyhydric alcohol. Examples of starting polyhydric alcohols are hydrogenated bisphenol A, 1,4-butanediol,
It contains neopentyl glycol, polyoxyalkylene glycol, trimethylolpropane and the like, and is similarly obtained by reaction with epichlorohydrin.

Polyglycidyl polycarboxylic acid ester:
This type of epoxy compound is also known as one type of epoxy resin. Diglycidyl phthalate and hydrogenated diglycidyl phthalate are examples.

N, N-di- (2,3-epoxypropyl) derivatives of aromatic amines: Epoxy compounds of this type include aromatic compounds such as aniline, toluidine, methylenebis (4-aminobenzene) and m-aminophenol. It is obtained by reacting an amine with epichlorohydrin.

2,3-Epoxypropyl isocyanurate: Includes mono-, di- and triesters. Triesters are preferred. Compounds with too high an epoxy equivalent need to be added in large amounts to the resin in order to obtain an effective level of epoxy group concentration, which adversely affects the flame retardancy and other physical properties of the molded article.

(B-2) Organotin compounds: di-n-butyltin maleate polymer, di-n-octyltin maleate polymer, di-n-butyltin-3-mercaptopropionate, di-n-octyltin- 3-mercaptopropionate, di-n-butyltin mercaptoacetate, diethylene glycol bis (butyltin thioacetate), dibutyltin sulfide, dioctyltin sulfide, dibutyltin dioctylmercaptide, dimethyltin (ethylene glycol monothioglycolate) and the like.

(B-3) Chelating agent: phosphite triester: aliphatic phosphite such as trioctyl phosphite, tridecyl phosphite, tridodecyl phosphite; triphenyl phosphite, trisnonyl phenyl phosphite, tris Aromatic phosphites such as t-butylphenyl phosphite; aliphatic and aromatic mixed phosphites such as diphenyloctyl phosphite and diphenylisodecyl phosphite; bisphenol A-
Bisdialkyl phosphite, dialkyl pentaerythritol diphosphite, 2,2'-methylenebis-di-t-butylphenyloctyl phosphite, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene and the like Other phosphites.

Phosphoric acid mono- or diesters or metal salts thereof: having 1 to 2 carbon atoms as the alcohol moiety of the ester
Aliphatic alcohols, phenols which may have a substituent such as an alkyl group, mono-phosphates of phosphoric acid having ethylene oxide adducts of these alcohols or phenols
Or diesters, and L of these phosphate esters
i, Na, K, Mg, Cu, Ca, Sr, Ba, Zn,
Metal salts such as Al.

Condensed phosphates: sodium pyrophosphate, potassium pyrophosphate, sodium acid pyrophosphate, sodium acid metaphosphate, sodium tripolyphosphate, sodium hexametaphosphate and the like.

Diphosphonic acid or its metal salt: hydroxyethylidene-1,1-diphosphonic acid, its alkali metal salt and alkaline earth metal salt.

Triazole chelate compound: 3- (N
-Salicyloyl) amino-1,2,4-triazole,
4-salicylideneimino-3,5-diphenyl-1,
2,4-triazole, 3,5-bis (4-amino-
1,2,4-triazole) and the like.

Hydrazine chelate compound: N, N'-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) proonyl] hydrazine, decanedicarboxylic acid disalicyloyl hydrazide, decanedicarboxylic acid di-
N'-butylsalicyloyl hydrazide and the like.

Polycarboxylic acids or metal salts thereof: succinic acid, fumaric acid, citric acid, tartaric acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, alkali metal salts and alkaline earth metal salts thereof.

The above epoxy compounds, organotin compounds and chelating agents can be added alone or in combination to the brominated flame retardant. The amount added is 0. 0 of brominated flame retardant.
01 to 50% by weight, that is, 0.01 to 50 parts by weight per 100 parts by weight of the flame retardant. Naturally, if the amount is too small, it is not enough to inhibit the reaction with iron oxide. It must be avoided because it is so large that it adversely affects

The method of blending with the brominated flame retardant is a dry method, that is, the flame retardant and the inhibitor component are uniformly mixed using a conventional mixer such as a Henschel mixer, a speed mixer, a V-type blender, a Nauta mixer, or a conical mixer. Can be adopted. If it is difficult to obtain a uniform mixture by the dry method depending on the type and amount of the inhibitor component, the wet method is preferably employed. For example, a method of dissolving, dispersing or emulsifying an inhibitor component in water or a solvent, mixing this liquid with a flame retardant and then drying the mixture, adding the inhibitor component to a slurry of the flame retardant in water or a solvent, mixing, and then filtering. For example, a method of drying the obtained cake.

Typical examples of the thermoplastic resin for which the flame retardant of the present invention is used include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, HI-PS resin,
All other flammable thermoplastics, including but not limited to ABS resins, ethylene-vinyl acetate resins (EVA) and their polymer blends.

The method of use is the same as the case of using the contained bromine-containing flame retardant alone to make the thermoplastic resin flame-retardant.

[0033]

Example 1 While mixing 1 kg of tetrabromobisphenol A-bisdibromopropyl ether (TBBA-BDBPE) with a speed mixer, bisphenol A diglycidyl ether (Adekaizer EP1 manufactured by Asahi Denka Kogyo KK) was used.
7; 10 g of a 10% isopropyl alcohol solution having an epoxy equivalent of 190) was added thereto, followed by mixing for further 10 minutes, followed by drying with a blow dryer at 60 ° C. for 6 hours to obtain a flame retardant composition. The loss on heating of this composition at 130 ° C. for 2 hours was 0.07%. The 1% and 5% weight loss temperatures of a 20: 1 weight ratio mixture of this composition and iron oxide were measured and the results shown in Table 2 were obtained.

Next, the following composition: raw material parts by weight ───────────────────── HI-PS resin (Nippon Steel Chemical Co., Ltd.) (100 Estyrene H-65 manufactured by Co., Ltd.) The flame retardant composition of the present invention 7 A mixture of antimony trioxide 2 Irganox 1010 0.1 was mixed with a Henschel mixer and kneaded with a twin-screw extruder set at 200 ° C. The test resin pellets were manufactured, and the pellets were tested for flame retardancy and iron oxide stability. Table 2 shows the results.

Example 2 800 g of TBBA-BDBPE and 200 g of tetrabromobisphenol A diglycidyl ether type epoxy resin oligomer (epoxy equivalent: 750) were mixed for 10 minutes using a speed mixer to obtain a flame retardant composition. 1
The loss on heating at 30 ° C. for 2 hours was 0.12%.

This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained. However, the 1% and 5% weight loss temperature readings of the mixture with iron oxide are based on the TBBA in the composition.
-The values were reduced by 0.8% and 4%, respectively, for conversion to the BDBPE content.

Example 3 While 1 kg of TBBA-BDBPE was mixed with a speed mixer, 2 g of tetra (tridecyl) -4,4'-isopropylidenediphenyldiphosphite (JA-805 manufactured by Johoku Chemical Co., Ltd.) was added, and 30 Mix for a minute,
A flame retardant composition was obtained.

The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 4 1 kg of TBBA-BDBPE and 10 g of 3- (N-salicyloyl) amino-1,2,4-triazole (Adeka Stab CDA-1M manufactured by Asahi Denka Kogyo KK) were mixed using a speed mixer. A flame retardant composition was obtained.

This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 5 10 g of a 1: 1 aqueous methanol solution containing 50% by weight of a mono-di-mixed phosphoric acid ester monoester salt of 8 mol of distyrenated phenol ethylene oxide while mixing 1 kg of TBBA-BDBPE with a speed mixer.
Was sprayed. Thereafter, the resultant was dried with a blow dryer at 60 ° C. for 6 hours to obtain a flame retardant composition having a loss on heating of 130 ° C. × 2 hours of 0.15%.

This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained. However, for the measurement of the 1% and 5% weight loss temperatures, the composition was further dried until the weight loss on heating at 130 ° C. × 2 hours became 0.08%.

Example 6 While stirring 1 kg of TBBA-BDBPE in a Henschel mixer, 20% of hydroxyethylidene-1,1-diphosphonic acid (Chelate 101 manufactured by Yokkaichi Gosei Co., Ltd.) was added.
100 g of an aqueous solution (adjusted to pH 6 with NaOH) is added,
After further mixing for 3 minutes, the mixture was dried with a blow dryer at 60 ° C. to obtain a flame retardant composition having a heating loss of 0.1% at 130 ° C. × 2 hours.

The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 7 1 kg of TBBA-BDBPE was dispersed in 1 L of isopropyl alcohol using a homomixer. To this, 100 g of a 10% aqueous solution of nitrilotriacetic acid disodium salt was gradually added dropwise, and after completion of the addition, the mixture was filtered with a 5B filter paper and dried with a blower at 60 ° C. to obtain a flame retardant composition.

The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 8 1 kg of TBBA-BDBPE and 10 g of dibutyltin maleate polymer (mp. 105-125 ° C.) were mixed in a speed mixer to obtain a flame retardant composition.

The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 9 1 kg of hexabromocyclododecane (HBCD) and α
10 g of a 10% solution of olefin (C18-22) epoxide in isopropanol is mixed in a speed mixer, dried in a blast drier at 60 ° C., and has a loss on heating of 130 ° C. × 2 hours of 0.06%. A flame retardant composition was obtained.

This composition was formulated as follows: parts by weight of raw material ───────────────────── HI-PS resin (Nippon Steel Corporation) (100 Estyrene H-65 manufactured by Chemical Co., Ltd.) The flame retardant composition of the present invention 3.5 was mixed in a Henschel mixer according to Irganox 1010 0.2, kneaded with a twin screw extruder set at 200 ° C., and tested. Resin pellets were produced.

A test piece molded from the pellet was subjected to a flame retardancy test and an iron oxide resistance stability test in the same manner as in Example 1, and the results shown in Table 3 were obtained. However, in the iron oxide stability test, the mixing amount of iron oxide was changed to 5% by weight of the pellet.

Example 10 1 kg of HBCD and sesquilauryl phosphate 1
200 g of a 0% isopropyl alcohol solution was mixed in a speed mixer, dried with a blast dryer at 60 ° C, and dried at 130 ° C.
A flame retardant composition having a heat loss of 0.08% for 2 hours was obtained.

The composition was tested in the same manner as in Example 9 and the results shown in Table 2 were obtained.

Example 11 After mixing 1 kg of HBCD and 100 g of a 30% aqueous slurry of calcium sesquiphenyl phosphate ester in a speed mixer, the mixture was dried with a blow dryer at 60 ° C.
A flame retardant composition having a loss on heating of 130 ° C. for 2 hours of 0.12% was obtained.

This composition was tested in the same manner as in Example 9, and the results shown in Table 3 were obtained. However, for the measurement of the 1% and 5% weight loss temperatures, the composition was further dried at 60 ° C. until the weight loss on heating at 130 ° C. × 2 hours became 0.05%.

Example 12 1 kg of HBCD and 10 g of dioctyltin maleate polymer (mp. 91 to 101 ° C.) were mixed with a speed mixer to obtain a flame retardant composition. 130 ° C. of the composition
The loss on heating for 2 hours was 0.06%.

This composition was tested in the same manner as in Example 9, and the results shown in Table 3 were obtained.

Comparative Example 1 In Example 1, the loss on heating at 130 ° C. × 2 hours was 0.
Same as Example 1 except that 05% TBBA-BDBPE bulk powder was used.

Comparative Example 2 In Example 9, the loss on heating at 130 ° C. for 2 hours was 0.
Same as Example 9 except that 08% HBCD bulk powder was used.

[0060]

[Test method] Flame retardancy test: Test resin pellets at 200 ° C
The test piece was molded into a UL-94 flame-retardant test piece (1/8 inch thick) using an injection molding machine set as described above, and tested by the UL-94 flame-retardant test method.

Iron oxide resistance stability test: resin pellet 100
And ₂ parts of Fe ₂ O ₃ (Examples 1 to 8 and Comparative Example 1) or 5 parts (Examples 9 to 12 and Comparative Example 2) were mixed with a Henschel mixer, and 200 kg / cm ² , 230 ° C. × 20 minutes Was pressed into a test piece having a thickness of 1/16 inch under the conditions described in the above, and cooled by a cold press for 5 minutes. The obtained test piece was divided into two parts, one was at room temperature in a silica gel desiccator, and the other was R
Each was stored for 5 days in a constant temperature and humidity oven at 80% H and a temperature of 40 ° C., and the surface condition was observed and evaluated according to the following criteria. 〇: There was no difference between the two in the surface state immediately after molding. Δ: No change was observed in the sample stored in the desiccator, and blistering occurred in the sample stored in the constant temperature and humidity oven. ×: Voids or sink marks were generated on the surface immediately after molding, and those stored in a constant-temperature and constant-humidity oven blistered.

[0062]

[Table 2]

[0063]

[Table 3]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H028 AA07 AA28 AA29 AA30 AA35 4J002 AA011 BH022 CD042 CD082 CD132 CD142 EB096 EB136 EJ056 EL027 EQ027 EU167 EU196 EV066 EW067 EW127 EZ017 EZ067 FD136 FD202 FD

Claims (5)

[Claims] 1. A flame retardant composition having iron oxide resistance for a thermoplastic resin molded using a device which may come into contact with iron oxide, comprising: (a) 130 flame retardant alone. The heat loss at 2 ° C. × 2 hours was 0.1% by weight or less, and the mixture of the flame retardant and iron oxide at a weight ratio of 20: 1 was analyzed by differential thermal analysis (air-heating rate: 10 ° C./min) in an air stream. A bromine-containing flame retardant whose measured 1% and 5% weight loss temperatures are at least 30 ° C. respectively lower than the 1% and 5% weight loss temperatures measured by differential thermal analysis of the flame retardant alone under the same conditions; and A flame retardant composition comprising an epoxy compound, an organotin compound, a chelating agent or a mixture thereof having an epoxy equivalent of 1000 or less at 0.01 to 50% by weight of the flame retardant. 2. The brominated flame retardant (a) is selected from tetrabromocyclooctane, hexabromocyclododecane, tribromophenyl-dibromopropyl ether, tribromophenyl-1,2-dibromo-2-methylpropyl ether, 2. The composition of claim 1 wherein the composition is selected from bisphenol A-bisdibromopropyl ether, tetrabromobisphenol S-bisdibromopropyl ether and trisdibromopropyl isocyanurate. 3. The epoxy compound according to claim 1, wherein said epoxy compound has 8 to 30 carbon atoms.
Olefin epoxide, epoxidized unsaturated fatty acid triglyceride, polyglycidyl ether of polyhydric phenol,
Polyglycidyl ether of polyhydric alcohol, polyglycidyl ester of polycarboxylic acid, N, N of aromatic amine
3. The composition according to claim 1, wherein the composition is selected from -di- (2,3-epoxypropyl) derivatives and isocyanuric acid 2,3-epoxypropyl ester. 4. The organic tin compound is di-n-butyltin maleate polymer, di-n-octyltin maleate polymer, di-n-butyltin-3-mercaptopropionate, di-n-octyltin-3-ion. Mercaptopropionate, di-n-butyltin mercaptoacetate,
3. The composition according to claim 1, wherein the composition is selected from diethylene glycol bis (butyltin thioacetate), dibutyltin sulfide, dioctyltin sulfide, dibutyltin dioctylmercaptide and dimethyltin (ethylene glycol monothioglycolate). 5. The chelating agent is a phosphite triester, a phosphate mono- or diester or a metal salt thereof,
The composition according to claim 1, wherein the composition is selected from condensed phosphate, diphosphonic acid or a metal salt thereof, a triazole chelate compound, a hydrazine chelate compound, and a polycarboxylic acid or a metal salt thereof.