JPH0977962A - Stabilized flame-retardant polyalkylene terephthalate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition remarkably improved in heat stability and discoloration resistance by adding epoxypropyl isocyanurate to a polyalkylene terephthalate resin blended with a brominated flame retardant. SOLUTION: This resin composition is obtained by adding 0.01-5.0 pts.wt. epoxypropyl isocyanurate to a flame-retardant polyalkylene terephthalate resin comprising a blend of 100 pts.wt. polyalkylene terephthalate resin with 1-50 pts.wt. brominated flame retardant. The addition of at least one compound selected from epoxypropyl isocyanurate and hydrotalcite, zinc-substituted hydrotalcite compounds, type A zeolite and a zeolite containing a group II or IV metal to the composition can further remarkably improve the heat stability and discoloration resistance thereof. An example of the epoxypropyl isocyanurate used is tris(epoxypropyl) isocyanurate which produces a particularly desirable effect.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a stabilized flame-retardant polyalkylene obtained by adding a specific additive to a flame-retardant polyalkylene terephthalate resin comprising a polyalkylene terephthalate resin and a bromine flame retardant. The present invention relates to a terephthalate resin composition, and is widely used in a field where flame retardancy is required for a polyalkylene terephthalate resin.

[0002]

2. Description of the Related Art Generally, in order to make a polyalkylene terephthalate resin flame-retardant, a method of adding a flame retardant such as a halogen compound, a phosphorus compound, antimony trioxide or a flame retardant auxiliary has been conventionally performed. Among these flame retardants, halogen compounds, especially bromine compounds, are widely used.

However, in general, when a brominated flame retardant is added to a polyalkylene terephthalate resin,
It is known that the thermal stability of the flame-retardant polyalkylene terephthalate resin is remarkably reduced, and the following technique has been already disclosed in order to suppress the reduction of the thermal stability.

(1) A technique of adding an epoxy compound to a flame-retardant aromatic polyester resin (JP-A-61-28)
5250). The epoxy compound used here is a polyfunctional epoxy compound, and preferred examples thereof include a bisphenol type epoxy compound obtained by reacting bisphenol A and epichlorohydrin at various ratios, and a novolak resin and novolak obtained from epichlorohydrin. Type epoxy compound, polyglycidyl esters obtained from polycarboxylic acid and epichlorohydrin, alicyclic compound type epoxy compound obtained from alicyclic compound (eg, dicyclopentadiene), aliphatic compound having alcoholic hydroxyl group (eg, butanediol) ,
Glycidyl ethers obtained from epichlorohydrin, epoxidized polybutadiene, glycidyl methacrylate, and other epoxy-containing unsaturated monomers, and other unsaturated monomers such as ethylene. Etc., but these are not isocyanurates having an epoxy group, and more specifically, it is a technique using an epoxy compound which is completely different from the epoxypropyl isocyanurate used in the present invention. There is no description or suggestion of a technique for stabilizing isocyanurate by using it in a flame-retardant polyalkylene terephthalate resin.

The novolac type epoxy compound used here is an epoxy compound obtained from a novolac resin and epichlorohydrin, and although there is no further detailed description here, it is generally described in the literature ("Epoxy Resin Handbook"). As shown in “Masaki Shinbo, published by Nikkan Kogyo Shimbun, page 61), the following formula

[0006]

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A phenol novolac type epoxy resin represented by

[0008]

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The cresol novolac type epoxy resins represented by the following are epoxy resins using phenol novolac or cresol novolac as a raw material. Therefore, it does not include an epoxy resin using a novolac other than phenol novolac or cresol novolac as a raw material, or a blend polymer composed of a mixture thereof.

(2) A technique of adding an epoxy compound, an inorganic filler, and a salt containing an alkali or alkaline earth metal cation to a thermoplastic polyester resin (Japanese Patent Laid-Open No. 5-209117). It is described that a flame retardant can be added to the thermoplastic polyester resin, but no examples thereof are found. Here, tris (epoxypropyl) isocyanurate is also exemplified as the epoxy compound, but it is not a technique of adding tris (epoxypropyl) isocyanurate alone. The salt containing an alkali or alkaline earth metal cation is a salt which is completely different from the hydrotalcites and zeolites used in the present invention.

(3) Further, a technique of adding hydrotalcite to a flame-retardant aromatic polyester resin (Japanese Patent Application Laid-open No. Sho 6-66).
0-1241). This is a technique to improve the occurrence of corrosion during molding, yellowing of molded products, heat resistance deterioration, and weather resistance deterioration by adding hydrotalcite alone, and hydrotalcite and epoxypropyl isocyanurate compound It is not a technique for heat stabilization by combined use of, and there is no such suggestion.

(4) Further, a technique of adding A-type zeolite to a flame-retardant aromatic polyester resin to heat-stabilize it (JP-A-62-199654). This is also a technique for thermally stabilizing A type zeolite alone, not a technique for thermally stabilizing A type zeolite and an epoxypropyl isocyanurate compound in combination. Absent.

[0013]

Problems to be Solved by the Invention JP-A-61-2852
In the conventional technique of adding the polyfunctional epoxy compound as described in No. 50 and the above-mentioned hydrotalcite or A-type zeolite alone, sufficient thermal stabilization against severe heat history during molding is still achieved. No effect is obtained, and even if these hydrotalcites and A-type zeolite are added in combination, a sufficient heat stabilizing effect cannot be obtained, and further development of additives having excellent heat stabilizing effect is awaited. It was

[0014]

From such a viewpoint, the inventors of the present invention are keen on an additive having an excellent heat stabilizing effect for a flame-retardant polyalkylene terephthalate resin composed of a polyalkylene terephthalate resin and a bromine flame retardant. As a result of repeated research, a flame-retardant polyalkylene terephthalate resin composition stabilized by adding epoxypropyl isocyanurate to a flame-retardant polyalkylene terephthalate resin composed of a polyalkylene terephthalate resin and a bromine flame retardant is disclosed. It has been found that the thermal stability and the color resistance are significantly improved. Furthermore, at least one compound selected from the group consisting of epoxypropyl isocyanurate and hydrotalcite, zinc-substituted hydrotalcite compounds, A-type zeolite and zeolite containing a metal of Group II or IV of the periodic table. The present invention has been completed by finding that the thermal stability and the coloring resistance of the resin composition stabilized by the combined use are further improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The alkylene group of the polyalkylene terephthalate resin used in the present invention has 2 to 6 carbon atoms.
An alkylene group of, for example, ethylene,
Examples thereof include groups such as propylene, butylene and hexylene. Examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin (hereinafter, "PE
"T resin". ), Polypropylene terephthalate resin, polybutylene terephthalate resin (hereinafter referred to as “PBT
It is called "resin". ) And polyhexylene terephthalate resin, preferably PET resin and PB
T resin can be mentioned.

These polyalkylene terephthalate resins are usually used alone, but if necessary, two or more of them can be used in combination.

Further, the addition of glass fiber to the polyalkylene terephthalate resin used in the present invention causes no problem and does not affect the heat stabilizing effect.

As the bromine-based flame retardant used in the present invention, any bromine-based flame retardant commonly used in this field can be used without limitation. Among these, a brominated bisphenol A-based flame retardant is commonly used. Examples thereof include carbonate oligomers, brominated bisphenol A-based epoxy resins, brominated styrene-based, brominated phthalimide-based and brominated phenoxytriazine-based flame retardants.

The brominated bisphenol A-based carbonate oligomer has 1 to 8 bromine atoms and 1 carbonyloxy group (-C (O) O-) in the residue obtained by removing H from -OH group of bisphenol A. An oligomer having a degree of polymerization (n) of 1 to 10 is a polymer of a group to which is bonded. For example, a flame retardant represented by the following formula can be given.

[0020]

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Commercially available flame retardants of the above formula include:
"Fireguard 7000" and "Fireguard 7500" from Teijin Kasei KK can be mentioned.

[0022]

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Commercially available flame retardants of the above formula include:
Great Lakes Chemical Co., Ltd. “Great
Lakes BC-52 "and" Great Lake.
sBC-58 "can be mentioned.

The brominated bisphenol A type epoxy resin has 1 to 8 bromine atoms and one 2-hydroxypropylene group (-CH ₂ CH (OH) in the residue obtained by removing H from -OH group of bisphenol A. ) CH ₂ -)-bonded polymer of which end is free of epoxy group

[0025]

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Examples of the resin include those having a degree of polymerization (n) of 1 to 100. For example, a flame retardant represented by the following formula can be given.

[0027]

[Chemical 6]

Commercially available flame retardants of the above formula include:
There are various products depending on the degree of polymerization, and "F-2300" and "F-2300" of Bromochem Far East Co., Ltd.
"H", "F-2400" and "F-2400E", "Prasam EP-16" manufactured by Dainippon Ink and Chemicals, Inc.,
"Prasam EP-30", "Prasam EP-10"
0 "and" Prasam EP-500 "," SR-T1000 "," SR-T200 "of Sakamoto Pharmaceutical Co., Ltd.
0 "," SR-T5000 "and" SR-T2000 "
0 "and the like.

Further, as an example of the brominated bisphenol A type epoxy resin, 1 to 8 bromine atoms and 1 2-hydroxypropylene group (--CH 2) are added to the residue obtained by removing H from the --OH group of bisphenol A. ₂ CH (OH) CH ₂
The compound in which the epoxy group at the terminal of the polymer of the group to which-) is bonded is blocked with a blocking agent can be mentioned.
The blocking agent is not limited as long as it is a compound capable of ring-opening addition of an epoxy group, and examples thereof include those containing a bromine atom in phenols, alcohols, carboxylic acids, amines and isocyanates, Among them, brominated phenols are preferable in terms of improving the flame retardant effect, and dibromphenol, tribromophenol, pentabromophenol, dibromoethylphenol, dibromopropylphenol, dibromobutylphenol, dibromocresol and the like can be mentioned. Can be done. Examples of the flame retardant in which the terminal epoxy group of the polymer is blocked with a blocking agent include the flame retardant represented by the following formula.

[0030]

[Chemical 7]

Commercially available flame retardants of the above formula include:
"Prasam EC-1" by Dainippon Ink and Chemicals, Inc.
4, "Prasam EC-20" and "Prasam EC"
-30 ", Toto Kasei Co., Ltd.'s" TB-60 "and" TB
-62 "," SR-T3040 "of Sakamoto Pharmaceutical Co., Ltd.
And "SR-T7040".

The brominated styrene flame retardant has a styrene skeleton.

[0033]

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Brominated styrene monomer having 1 to 5 bromine atoms bonded to the benzene ring of

[0035]

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And its polymer

[0037]

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It is preferably a polymer. For example, bromstyrene and brominated polystyrene can be mentioned. Examples of commercially available brominated polystyrene flame retardants include "Pyrocheck 68P" manufactured by Ferro Corporation.
B ”,“ Gre ”of Great Lakes Chemical Co., Ltd.
at Lakes PDBS-10 "and" Great
Lakes PDBS-80 "and the like.

The brominated phthalimide flame retardant is 1 to 8
A compound in which one bromine atom is bonded to the benzene ring of one or two phthalimide groups, for example, ethylene bis (tetrabromophthalimide) of the following formula

[0040]

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Examples of commercially available flame retardants include “Saytex B” manufactured by Albemarle Corporation.
"T-93W" and "Saytex BT-93" can be mentioned.

The brominated phenoxytriazine flame retardant is a compound in which 1 to 5 bromine atoms are bound to a phenoxy group, and 1 to 3 of the brominated phenoxy groups are bound to a triazine ring, for example, Tris. (Dibromophenoxy) triazine and tris (tribromophenoxy) triazine of the formula

[0043]

[Chemical 12]

Examples of the commercially available flame retardant of the above formula include "Piroguard SR-245" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

In the examples, typical brominated flame retardants widely used among these are used, but the same effect can be obtained even if the other brominated flame retardants mentioned above are used. There is expected.

In addition to the bromine-based flame retardants commonly used as described above, the bromine-based flame retardants listed in the literature and catalogs of bromine-based flame retardant manufacturers can also be used. It is fully expected that the flame-retardant polyalkylene terephthalate resin composition containing a flame retardant can achieve the effects of the present invention in a comparable manner. Examples of the brominated flame retardants include brominated alkanes, brominated cycloalkanes, brominated isocyanates, brominated benzenes, brominated phenols, brominated maleimides, brominated phthalic acids and brominated bisphenol A.
Examples thereof include monomers and oligomers thereof.

The brominated alkane is a compound in which 1 to 8 bromine atoms are bonded to an alkane (chain aliphatic hydrocarbon) having 2 to 6 carbon atoms. Examples of the alkane include ethane, propane, butane, pentane and hexane, and examples of the brominated alkane include dibromethane, tetrabromethane, tribrompropane, tetrabrombutane and octabromhexane. You can

Brominated cycloalkanes are hydrocarbons having 1 to 6 bromine atoms bonded to a cycloalkane having 6 to 12 carbon atoms (cycloaliphatic hydrocarbon). Examples of the cycloalkane include cyclohexane and cyclododecane, and examples of the brominated cycloalkane include hexabromocyclohexane and hexabromocyclododecane.

The brominated isocyanates are obtained by the alkyl residue of the above-mentioned brominated alkane and isocyanic acid residue -N =
The compound which C = O couple | bonded and the compound which the brominated phenoxy group which 1-5 bromine atoms couple | bonded with the phenoxy group, and the isocyanic acid residue -N = C = O couple | bonded can be mentioned. Specific examples thereof include tris (2,3-dibromopropyl) isocyanurate, tris (dibromophenoxy) isocyanurate, tris (dibromoethylphenoxy) isocyanurate, tris (tribromophenoxy) isocyanurate and tris (dibromophenoxy) isocyanurate. Examples thereof include bromopropylphenoxy) isocyanurate.

Brominated benzenes are compounds consisting of a group in which one or more bromine atoms are bonded to a benzene ring, and include tetrabromobenzene, hexabromobenzene, bromophenylallyl ether, pentabromotoluene,
Examples thereof include bis (pentabromophenyl) ethane and poly (pentabromobenzyl acrylate).

Brominated phenols are compounds in which one or more bromine atoms are bonded to a phenol group, a phenyl ether group and a benzyl group, and examples thereof include dibromophenol, tribromophenol and 2,3-dibromo. Examples thereof include propyl pentabromophenyl ether, bis (tribromophenoxy) ethane, pentabromophenylpropyl ether, hexabromodiphenyl ether, decabromodiphenyl ether, octabromodiphenyl ether and polydibromophenylene oxide.

The brominated maleimide is a compound in which 1 to 5 bromine atoms are bonded to a maleimide group, and examples thereof include tribromophenylmaleimide. Examples of brominated phthalic acids include compounds in which 1 to 4 bromine atoms are bonded to phthalic acid, and examples thereof include tetrabromophthalic anhydride.

Examples of the brominated bisphenol A monomer or brominated bisphenol S monomer include compounds in which 1 to 8 bromine atoms are bonded to the bisphenol A compound or the bisphenol S compound, and examples thereof include: Tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetrabromobisphenol A bis (2,3
-Dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), tetrabromobisphenol S and tetrabromobisphenol S bis (2,3-dibromopropyl ether) Etc. can be mentioned.

The amount of the bromine-based flame retardant used in the present invention varies variously depending on the degree of flame retardancy required for the polyalkylene terephthalate resin and the physical properties thereof. Terephthalate resin 1
1 to 50 parts by weight is used with respect to 00 parts by weight. If it is less than 1 part by weight, the desired flame retardancy cannot be imparted, and if it exceeds 50 parts by weight, the physical properties of the molded product of the resin composition are impaired, but it is not preferable. However, from the balance of flame retardancy and physical properties, practically 1
It is used in the range of 0 to 25 parts by weight.

Depending on the purpose, a bromine-based flame retardant may be used.
More than one kind can be used in combination, but usually one kind is sufficient.

It is often practiced to use a flame retardant aid such as antimony trioxide together for the purpose of further increasing the flame retardancy, but the addition of this flame retardant aid has no effect on the effect of the present invention. Does not give. The addition amount of the flame retardant aid is usually 1 to 20 parts by weight with respect to 100 parts by weight of the polyalkylene terephthalate resin, but in view of the physical properties and the like, the preferable amount is 2 to 5 parts by weight. is there.

The epoxypropyl isocyanurate used in the present invention has the general formula (1)

[0058]

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[In the formula (1), at least one of R ^{5 to} R ⁷ is an epoxy group.

[0060]

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And the others may be hydrogen atoms. ] Can be mentioned. Specific examples of epoxypropyl isocyanurate include mono (epoxypropyl) isocyanurate and bis (epoxypropyl).
Examples thereof include isocyanurate and tris (epoxypropyl) isocyanurate. Among them, tris (epoxypropyl) isocyanurate can be mentioned as a compound that brings a preferable effect for improving the thermal stability of the flame-retardant polyalkylene terephthalate resin. .

The hydrotalcite used in the present invention is a compound composed of magnesium and aluminum. For example, the general formula (2) Mg _1-x Al _x (OH) ₂ (A ^q- ) _{x / q.} An example is a compound represented by aH ₂ O (2).

The zinc-substituted hydrotalcite compound is, for example, a compound obtained by substituting Zn for a part of Mg in the general formula (2), and has the general formula (3) [Mg _y1 Zn _y2 ] _{1- x Al x (OH) 2 (} a q-) x / q · aH 2 O (3) compounds can be mentioned. The substitution ratio of Zn is 1 mol% to 50 mol%, preferably 15 mol% to 30 mol% with respect to Mg.

[In the formulas (2) and (3), q is 1 or 2
In and, A ^q- is q-valent anion, i.e. (CO ₃₎ ^2- or (ClO ₄₎ ^- a is, x, y1, y2 and a represents a real number, each satisfying the following conditions.

0 <x ≦ 0.5, y1 + y2 = 1−x, y1 ≧
y2, 0 ≦ a <1].

The following are typical examples of the general formula (2). No. 1; Mg _0.750 Al _0.250 (OH) ₂ (CO ₃ ) _0.125 / 0.5 H ₂ O No. 2; Mg _0.692 Al _0.308 (OH) ₂ (CO ₃ ) _0.154 / 0.1 H ₂ O No. 3; Mg _0.683 Al _0.317 (OH) ₂ (CO ₃ ) _0.159 / 0.5 H ₂ O No. 4; Mg _0.667 Al _0.333 (OH) ₂ (CO ₃ ) _0.167 / 0.1 H ₂ O No. 5; Mg _0.750 Al _0.250 (OH) ₂ (ClO ₄ ) _0.250・ 0.5 H ₂ O No. 6; Mg _0.692 Al _0.308 (OH) ₂ (ClO ₄ ) _0.308・ 0.1 H ₂ O No. 7; Mg _0.667 Al _0.333 (OH) ₂ (ClO ₄ ) _0.333・0.1 H ₂ O.

The following are typical examples of the general formula (3). No. 8; Mg _0.625 Zn _0.125 Al _0.250 (OH) ₂ (CO ₃ ) _0.125・_{0.45H 2} O No. 9; Mg _0.538 Zn _0.154 Al _0.308 (OH) ₂ (CO ₃ ) _0.154 No. 10; Mg _0.500 Zn _0.167 Al _0.333 (OH) ₂ (CO ₃ ) _0.167・ 0.54H ₂ O No. 11; Mg _0.625 Zn _0.125 Al _0.250 (OH) ₂ (ClO ₄ ) _0.250・ 0.3 H ₂ O No. 12; Mg _0.538 Zn _0.154 Al _0.308 (OH) ₂ (ClO ₄ ) _0.308・ 0.5 H ₂ O No. 13; Mg _0.500 Zn _0.167 Al _0.333 (OH) ₂ (ClO ₄ ) _0.333 · 0.1 H ₂ O.

In the present invention, in order to improve the compatibility and dispersibility of the hydrotalcite- and zinc-substituted hydrotalcite compound with the flame-retardant polyalkylene terephthalate resin, the hydrotalcite and zinc-substituted hydrotalcite compound A surface treatment agent of a talcite compound, for example, a surface treatment with a higher fatty acid is also frequently used. Specific examples of the hydrotalcite product include Alkamizer 2 and Alkamizer manufactured by Kyowa Chemical Industry Co., Ltd. 3 and DH
T-4A-2 and the like can be mentioned, and specific products of the zinc-substituted hydrotalcite compounds include Alkamizer 4 and Alkamizer 4-2 manufactured by Kyowa Chemical Industry Co., Ltd.
And Alcamizer 7 and the like.

Such surface-treating agents are not limited to the above-mentioned higher fatty acids, and are known in the literature, for example, JP-A-60-1241.
And those described on page 4, etc. As the surface treatment agent described in the known literature, those generally used in this field, for example, anionic surfactants, silane coupling agents, titanium coupling agents,
Examples thereof include higher fatty acid esters, and specific examples thereof include anionic surfactants such as sodium stearate, sodium oleate, and sodium laurylbenzenesulfonate, vinyltriethoxysilane, γ-aminopropyltriene. Silane-based or titanium-based coupling agents such as methoxysilane, isopropyltriisostearoyl titanate and isopropyltridecylbenzenesulfonyl titanate, and higher fatty acid esters such as glycerin monostearate and glycerin monooleate are shown.

[0070] As A-type zeolites used in the present invention have the general formula _{(4) Na 2 O · Al} 2 O 3 · 2SiO 2 · bH 2 O (4) wherein, b is 0 ≦ b ≦ 6 Indicates a real number. ] A type zeolite shown by these is mentioned, A natural zeolite or a synthetic zeolite may be sufficient. The A-type zeolite used includes higher fatty acids such as higher fatty acid alkali metal salts such as stearic acid and oleic acid, and organic sulfonic acids such as dodecylbenzene sulfonic acid. It may be surface-treated with such an organic sulfonic acid alkali metal salt.

The zeolite containing a metal of Group II or IV of the periodic table is a zeolite in which Na in the A-type zeolite is replaced with a metal of Group II or IV of the periodic table ( Hereinafter, referred to as "metal-substituted zeolite"), the metal is not particularly limited, magnesium, calcium, zinc, strontium, barium, zirconium and tin, etc. from the viewpoint of effect, toxicity and availability. Examples of preferable metals include calcium, zinc, magnesium, barium, and the like, and examples of the most preferable metals include calcium and zinc, which have excellent coloring resistance of the flame-retardant polyalkylene terephthalate resin. I can.

The metal substitution ratio of the A-type zeolite in the metal-substituted zeolite is preferably high, but normally, the one that can be easily obtained industrially has a substitution ratio of about 10 to 70 mol%. Is.

Specific examples of the metal-substituted zeolite include synthetic zeolites such as magnesium-substituted zeolite, calcium-substituted zeolite, zinc-substituted zeolite, strontium-substituted zeolite, barium-substituted zeolite, zirconium-substituted zeolite and tin-substituted zeolite, Further, natural zeolite having the metal can be used, and these A-type zeolite and metal-substituted zeolite can be used alone or in combination of two or more kinds.

Regarding the method for producing the above synthetic zeolite,
A known method may be used, for example, a production method described in JP-A-57-28145.

In order to improve the thermal stability of the flame-retardant polyalkylene terephthalate resin, a more preferable effect can be obtained by using it together with epoxypropyl isocyanurate.
Hydrotalcite, zinc-substituted hydrotalcite compounds and metal-substituted zeolite can be mentioned, and hydrotalcite can be mentioned as the one which brings the most preferable effect.

Among the epoxypropyl isocyanurates, particularly, by adding the above-mentioned hydrotalcite to tris (epoxypropyl) isocyanurate in combination, sample numbers 10 to 11 of [Example 1] and [Example 2] were obtained.
Nos. 11 to 12, No. 2 of [Example 3], Nos. 4 to 12 of [Example 4] and No. 4 of [Example 5], the flame-retardant polyalkylene terephthalate. The thermal stability of the resin can be improved.

Further, sample numbers 19 to 2 of [Example 1]
8, the same numbers 37 to 40, the same numbers 43 to 46, the same numbers 20 to 29, the same numbers 38 to 45, and the same number 4 of [Example 2].
8 to 49, the same number 7 to 10 and the same number 16 of [Example 3]
-18, the same number 21-22, the same number 31 of [Example 4]
~ 33, the same number 37 to 38, the same number 40, [Example 5]
No. 8-10, No. 14-16, and No. 18 of tris (epoxypropyl) isocyanurate and the hydrotalcite, zinc-substituted hydrotalcite, A-type zeolite, and metal-substituted zeolite The thermal stability of the flame-retardant polyalkylene terephthalate resin can be further improved by adding at least one compound selected from among them.

Further, by adding the above zinc-substituted hydrotalcite compound to tris (epoxypropyl) isocyanurate, the sample numbers 12 to 13 of [Example 1] and the same number 13 of [Example 2] were added. -14, the same number 3 in [Example 3], the same number 13-18 in [Example 4],
As shown in No. 5 of [Example 5], the thermal stability of the flame-retardant polyalkylene terephthalate resin can be improved.

Further, by adding the above-mentioned metal-substituted zeolite to tris (epoxypropyl) isocyanurate in combination, sample numbers 15 to 18 of [Example 1], 16 to 19 of [Example 2] and [No. Example 3] same number 5
To 6, the same numbers 25 to 30 of [Example 4], [Example 5]
As shown in No. 7 of the above, the thermal stability of the flame-retardant polyalkylene terephthalate resin can be improved.

Further, sample numbers 29 to 3 of [Example 1]
6, same numbers 41 to 42, same numbers 30 to 3 of [Example 2]
7, same numbers 46 to 47, same numbers 11 to 1 of [Example 3]
5, the same numbers 19 to 20, the same numbers 34 to 3 of [Example 4]
6, the same number 39, the same numbers 11 to 13 and the same number 17 of [Example 5], tris (epoxypropyl)
By adding at least two or more compounds selected from zinc-substituted hydrotalcite compounds, A-type zeolite, and metal-substituted zeolite to isocyanurate, the thermal stability of the flame-retardant polyalkylene terephthalate resin can be improved. It can be further improved.

Among the metal-substituted zeolites, calcium- and zinc-substituted zeolites are magnesium and barium as shown in sample numbers 16 to 17 of [Example 1] and 17 to 18 of [Example 2]. It can be preferably used because it is superior in coloring resistance as compared with the substituted zeolite.

The amount of the epoxypropyl isocyanurate used in the present invention is 0.01 to 5.0 parts by weight, preferably 0.05 to 3. parts by weight, based on 100 parts by weight of the polyalkylene terephthalate resin. 0 parts by weight.
If the addition amount is less than 0.01 part by weight, the heat stabilizing effect is not significantly observed, and if it is more than 5.0 parts by weight, the expected heat stabilizing effect is not observed, and it is used in the present invention. (A)
Among zeolites containing epoxypropyl isocyanurate and (b) hydrotalcite, (c) zinc-substituted hydrotalcite compound, (d) A-type zeolite, (e) metal of Group II or IV of the periodic table The addition amount of at least one compound selected from the above is 0.01 to 5.0 parts by weight of the component (a) and the components (b) to (e) with respect to 100 parts by weight of the polyalkylene terephthalate resin. )
At least one selected from the components is 0.01 to 5.
It is 0 part by weight, and preferably (a) component 0.05 to
3.0 parts by weight and components (b) to (e) 0.05 to
3.0 parts by weight.

The components (a) and (b) to (e)
When the addition amount of both components is less than 0.01 parts by weight, a more remarkable thermal stabilizing effect due to the combined addition is not observed, and the addition amounts of the components (a) and (b) to (e) are both 5. If it exceeds 0 parts by weight, the expected heat stabilizing effect due to the combined addition is not observed.

Here, there is no particular limitation on the combination ratio when the components (a) and (b) to (e) are used in combination, but the effective combination ratio is as follows:
The ratio of the component (a) to the components (b) to (e) is 98: 2% by weight to 2: 98% by weight.

When the combined use ratio of the component (a) is less than 2% by weight, the coloring preventing effect is not noticeable, and when it exceeds 98% by weight, the expected heat stabilizing effect by the combined use is not observed. .

The method of adding the specific additive used in the present invention to the flame-retardant polyalkylene terephthalate resin comprising the polyalkylene terephthalate resin and the bromine flame retardant may be carried out by a conventionally known technique. The flame-retardant polyalkylene terephthalate resin and the additive may be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer or the like, or one obtained by pre-packing the additive with the flame-retardant polyalkylene terephthalate resin. You may mix with the above-mentioned mixer.

Further, known stabilizers for these additives, for example, metal soaps, organic phosphorus compounds, antioxidants,
An ultraviolet absorber can be used together.

Further, if necessary, a lubricant, a pigment, a filler, a processing aid, a chlorinated flame retardant and the like can be added.

[0089]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In these examples, parts means parts by weight.

Component (a) [Epoxypropyl isocyanurate used in the present invention] A-1: mono (epoxypropyl) isocyanurate A-2: di (epoxypropyl) isocyanurate A-3: tris (epoxypropyl) isocyanate Nurate.

Component (b) [Hydrotalcite used in the present invention] B-1: Hydrotalcite represented by the formula No. 1 in the specification B-2: Represented by formula No. 4 in the specification Hydrotalcite B-3: Hydrotalcite represented by the formula No. 6 in the description.

Component (c) [Zinc-substituted hydrotalcite compound used in the present invention] C-1: Zinc-substituted hydrotalcite represented by formula No. 8 in the specification C-2: Formula in the specification Zinc-substituted hydrotalcite represented by No. 9 C-3: Zinc-substituted hydrotalcite represented by formula No. 11 in the specification.

[0093] Component (d) [A type zeolite used in the present _{invention] D-1: Na 2 O} · Al 2 O 3 · 2SiO 2 · 4.5 H 2
_{O D-2: Na 2 O} · Al 2 O 3 · 2SiO 2.

Component (e) [Metal-substituted zeolite used in the present invention] E-1: Magnesium-substituted zeolite E-2: Calcium-substituted zeolite E-3: Zinc-substituted zeolite E-4: Barium-substituted zeolite (E-1 to E-1) E-4 has a metal substitution rate of 70 mol%).

Component (f) [Additives other than the present invention] F-1: Bisphenol A type epoxy resin [Epicoat 1009 manufactured by Yuka Shell Epoxy Co., Ltd.] F-2: Novolac type epoxy resin [Okaka shell epoxy ( Co., Ltd. Epicoat 180S65] F-3: Diglycidyl hexahydrophthalate [Arbaldite CY184 manufactured by Ciba-Geigy] F-4: Magnesium silicate [2MgO · 6SiO ₂ · x]
H ₂ O] F-5: Magnesium aluminate [2.5 MgO · Al
₂ O ₃ · xH ₂ O] F-6: dawsonite _{[Al 2 O 3 · Na 2 O} · 2CO
₃ · xH ₂ O] F-7: aluminum silicate [Al ₂ O ₃ · 9SiO ₂ ·
xH ₂ O] F-8: Pyroaurite [Mg ₆ Fe ₂ (OH) ₁₆ C
O ₃ · 4H ₂ O] F-9: Barium sulfate F-10: zinc oxide F-11: sodium stearate.

Example 1 Polybutylene terephthalate resin [Teijin PBT resin C700 manufactured by Teijin Ltd.]
0] 100 parts, tetrabromobisphenol A carbonate oligomer [manufactured by Teijin Kasei Co., Ltd. Fireguard
7500] 20 parts and 5 parts of antimony trioxide were mixed with the additives shown in Tables 1 to 6, mixed with a Henschel mixer, and melt-kneaded at 230 ° C. using an extruder to obtain pellets. Furthermore, using this pellet, it is 52 m at 250 ° C.
A flat plate of m × 40 mm × 3 mm was injection molded. The obtained flat plate was cut into 25 mm × 20 mm, placed in a gear oven set at 255 ° C., and tested for a coloration state (coloring resistance) after 30 minutes and thermal stability until the color became brown.
The coloring state of the test piece was visually determined according to the following criteria. A: Light yellow, B: Light yellow, C: Yellow, D: Yellow-orange, E:
Light brown, F: brown The results are shown in Tables 1 to 6.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

Sample Nos. 1 to 46 are Examples and the same No. 47 to
99 is a comparative example. As is clear from the comparison of the results in Tables 1 to 6, the stabilized flame-retardant polyalkylene terephthalate resin composition of the present invention has extremely excellent thermal stability and coloring resistance. Recognize. When the components (a) and at least one of the components (b) to (e) are used in combination as in sample numbers 10 to 46, the same number 1 is obtained.
As compared with the case where only the component (a) such as ~ 9 is added,
It can be seen that the thermal stability and the coloring prevention effect are further excellent. When the addition amount of the component (a) is smaller than the addition amount of the present invention, as in the same numbers 47 to 49, the same numbers 50 to 50 are used.
When the component (a) is not added as in 86, the same number as 87
No. 90 to 98, when the additive (a) is used in combination with the additive other than the present invention, and the additive No. 99 is added. If neither is done, sufficient thermal stability and anti-coloring effect cannot be obtained.

[Example 2] 100 parts of polyethylene terephthalate resin [Sunpet manufactured by Asahi Kasei Kogyo Co., Ltd.], 15 parts of brominated epoxy resin [F-2300H manufactured by Bromochem Far East Co., Ltd.], 3 parts of antimony trioxide. , Polyethylene wax [Mitsui Petrochemical Industry Co., Ltd.
HI-WAX 405MP] (0.5 parts) was mixed with the additives shown in Tables 7 to 12, mixed with a Henschel mixer, and melt-kneaded at 250 ° C using an extruder to obtain pellets. Further, using these pellets, at 250 ° C., 52
A flat plate of mm × 40 mm × 3 mm was injection molded. The obtained flat plate was cut into 25 mm × 20 mm, placed in a gear oven set at 260 ° C., and tested for a coloration state (coloring resistance) after 30 minutes and thermal stability until the color became brown.
The coloring state of the test piece was judged according to the same criteria as in Example 1. The results are shown in Tables 7-12.

[0105]

[Table 7]

[0106]

[Table 8]

[0107]

[Table 9]

[0108]

[Table 10]

[0109]

[Table 11]

[0110]

[Table 12]

Sample Nos. 1 to 49 are Examples and the same No. 50 to
100 is a comparative example. As is clear from comparison of the results in Tables 7 to 12, the stabilized flame-retardant polyalkylene terephthalate resin composition of the present invention has extremely excellent thermal stability and coloring resistance. Recognize. still,
When the components (a) and at least one of the components (b) to (e) are used in combination as in sample numbers 7 to 49, the same number 1
Compared to the case where only the component (a) such as ~ 6 is added,
It can be seen that the thermal stability and the coloring prevention effect are further excellent. When the addition amount of the component (a) is smaller than the addition amount of the present invention as in the same numbers 50 to 52, the same number 53 to
When the component (a) is not added, as in 91, the same number 92
Like 95, even if the components (a) and at least one of the components (b) to (e) are used in combination, if the addition amount of each is less than the addition amount of the present invention, As described above, when an additive other than the present invention is added, when the component (a) is used in combination with an additive other than the present invention as shown in the same number 99, and when no additive is added like the same number 100, the However, sufficient thermal stability and anti-coloring effect cannot be obtained.

[Example 3] Polybutylene terephthalate resin [Tufpet N-101 manufactured by Mitsubishi Rayon Co., Ltd.]
0] 100 parts, brominated polystyrene [Pyrocheck 68PB manufactured by Ferro Co., Ltd.] 15 parts, and chlorinated polyethylene 3 parts were mixed with the additives shown in Tables 13 to 16 and mixed in a Henschel mixer. It was melt-kneaded at 230 ° C. to obtain pellets. Further, using this pellet, a flat plate of 52 mm × 40 mm × 3 mm was injection molded at 250 ° C. The obtained flat plate is cut into a size of 25 mm × 20 mm, placed in a gear oven set at 260 ° C., and
The coloring state (coloring resistance) after minutes and the thermal stability until deterioration to brown were tested. The coloring state of the test piece was judged according to the same criteria as in Example 1. The results are shown in Table 13 to Table 16.
Shown in

[0113]

[Table 13]

[0114]

[Table 14]

[0115]

[Table 15]

[0116]

[Table 16]

Sample Nos. 1 to 22 are Examples and the same No. 23 to
55 is a comparative example. As is clear from comparison of the results in Tables 13 to 16, the stabilized flame-retardant polyalkylene terephthalate resin composition of the present invention has extremely excellent thermal stability and color resistance. Recognize. still,
When the component (a) and at least one of the components (b) to (e) are used in combination as in sample numbers 2 to 22, the same number 1
It can be seen that the thermal stability and the anti-coloring effect are further excellent as compared with the case where only the component (a) is added. In addition, like (23) to (27), the components (a) and (b)
When used in combination with at least one of the components (e),
When the addition amount of the compound selected from the components (b) to (e) is smaller than the addition amount of the present invention, the same effect as the case where only the component (a) is added as in the same number 1 is obtained. I understand. When the amount of the component (a) added is less than that of the present invention, as in the same number 28, the same numbers 29 to 49 are used.
When the component (a) is not added as in the above, the same number 50 to 5
4, even if the component (a) and at least one of the components (b) to (e) are used in combination, the amount of the component (a) added is less than that of the present invention and the same number 55 as,
When no additive is added, neither sufficient thermal stability nor anti-coloring effect can be obtained.

[Example 4] Polybutylene terephthalate resin [PBT resin 1401 manufactured by Toray Industries, Inc.] 100
Part, ethylene bis (tetrabromophthalimide) [Saytex BT-93W manufactured by Albemarle Corporation] 18
Parts, 3 parts of antimony trioxide, 0.3 parts of MBS resin [Kane-Ace B-561 manufactured by Kanegafuchi Chemical Industry Co., Ltd.]
The additives shown in Tables 7 to 21 were mixed, mixed with a Henschel mixer, and then melt-kneaded at 230 ° C. using an extruder to obtain pellets. Furthermore, using this pellet, 250 ℃
Then, a flat plate of 52 mm × 40 mm × 3 mm was injection molded.
The obtained flat plate is cut into 25 mm × 20 mm and 260 ° C.
After being placed in a gear oven set to, the coloring state (coloring resistance) after 20 minutes and the thermal stability until deterioration to brown were tested. The coloring state of the test piece was judged according to the same criteria as in Example 1. The results are shown in Tables 17 to 21.

[0119]

[Table 17]

[0120]

[Table 18]

[0121]

[Table 19]

[0122]

[Table 20]

[0123]

[Table 21]

Sample Nos. 1 to 40 are Examples, and No. 41 to No.
72 is a comparative example. As is clear from the comparison of the results in Tables 17 to 21, the stabilized flame-retardant polyalkylene terephthalate resin composition of the present invention has extremely excellent thermal stability and coloring resistance. Recognize. still,
When the component (a) and at least one of the components (b) to (e) are used in combination as in sample numbers 4 to 40, the same number 1
Compared to the case where only the component (a) such as ~ 3 is added,
It can be seen that the thermal stability and the coloring prevention effect are further excellent. When the addition amount of the component (a) is smaller than the addition amount of the present invention as in the same numbers 41 to 43, the same number 44 to
When the component (a) is not added as in 61, the same number 62
Even when the component (a) and at least one of the components (b) to (e) are used in combination, the amount of the compound selected from the components (b) to (e) is When the amount is less than the addition amount of the component (b) to component (e), the additives other than the present invention and at least one component (b) to (e),
When used in combination with seeds, as in the same numbers 70 to 71, (a)
In the case where the components are used in combination with an additive other than the present invention and when the additive is not added as in the case of No. 72, neither sufficient thermal stability nor sufficient coloring preventing effect can be obtained.

[Example 5] Polyethylene terephthalate resin [Sanpet manufactured by Asahi Kasei Kogyo KK] 100 parts, tris (tribromophenoxy) triazine [Piroguard SR-245 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 20 parts, trioxide 5 parts of antimony and 0.3 parts of polyethylene wax [HI-WAX 400PF manufactured by Mitsui Petrochemical Industry Co., Ltd.] were mixed with the additives shown in Tables 22 to 25, mixed with a Henschel mixer, and then using an extruder. Melt kneading at 250 ° C. to obtain pellets. Furthermore, using this pellet,
A flat plate of 52 mm × 40 mm × 3 mm was injection molded at 250 ° C. The obtained flat plate is cut into 25 mm × 20 mm,
It was placed in a gear oven set at 240 ° C. and tested for a coloring state (coloring resistance) after 20 minutes and thermal stability until it deteriorates to brown. The coloring state of the test piece was judged according to the same criteria as in Example 1. The results are shown in Tables 22 to 25.

[0126]

[Table 22]

[0127]

[Table 23]

[0128]

[Table 24]

[0129]

[Table 25]

Sample Nos. 1 to 18 are examples, and No. 19 to 19 are the same.
55 is a comparative example. As is clear from the comparison of the results in Tables 22 to 25, the stabilized flame-retardant polyalkylene terephthalate resin composition of the present invention has extremely excellent thermal stability and coloring resistance. Recognize. still,
When the components (a) and at least one of the components (b) to (e) are used in combination as in sample numbers 4 to 18, the same number 1 is obtained.
Compared to the case where only the component (a) such as ~ 3 is added,
It can be seen that the thermal stability and the coloring prevention effect are further excellent. Further, when the addition amount of the component (a) is smaller than the addition amount of the present invention as in the same numbers 19 to 21, the same number 22 to
If the component (a) is not added as in item 36, the same number 37
Even if the component (a) and at least one of the components (b) to (e) are used in combination as described above, when the addition amount of the component (a) is less than the addition amount of the present invention, the same number 41 When adding an additive other than the present invention, as in
No. 49, when an additive other than the present invention is used in combination with a compound selected from the components (b) to (e), the components (a) and the additives other than the present invention are represented by the same numbers 50 to 54. When both and are used in combination and when no additive is added as in the case of the same number 55, neither sufficient thermal stability nor sufficient coloring preventing effect can be obtained.

[0131]

The flame-retarded polyalkylene terephthalate resin composition of the present invention has the following advantages in terms of heat stability and coloring resistance.
It is much better than the conventional flame-retarded polyalkylene terephthalate resin composition.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michihiro Kubo Sanyo Organic Synthesis Co., Ltd. 788 Kuchi, Takatsu-ku, Kawasaki-shi, Kanagawa

Claims (2)

[Claims] 1. A polyalkylene terephthalate resin 100.
Stabilized flame-retardant polyalkylene obtained by adding 0.01-5.0 parts by weight of epoxypropyl isocyanurate to a flame-retardant polyalkylene terephthalate resin composed of 1 part by weight and 1-50 parts by weight of bromine flame retardant. Terephthalate resin composition. 2. A polyalkylene terephthalate resin 100.
Parts by weight and 1 to 50 parts by weight of a bromine-based flame retardant in a flame-retardant polyalkylene terephthalate resin, (a) epoxypropyl isocyanurate 0.01 to
5.0 parts by weight and (b) hydrotalcite (c) zinc-substituted hydrotalcite compound (d) type A zeolite (e) selected from zeolites containing a metal of Group II or IV of the periodic table 0.01 of at least one compound
Stabilized flame-retardant polyalkylene terephthalate resin composition, which is obtained by adding together ~ 5.0 parts by weight.