JPH0258561A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition imparted with excellent flame- retardance without lowering the thermal stability and fluidity in molten state by compounding a thermoplastic polyester with a polycaprolactone, an organic halide, an antimony compound specific oxazoline compound. CONSTITUTION:The objective resin is produced by compounding (A) 100 pts.wt. of a thermoplastic polyester with (B) 0.1-30 pts.wt. of a terminal-blocked polycaprolactone, (C) 0.1-30 pts.wt. of an organic halide in terms of halogen element, (D) 0.1-20 pts.wt. of an antimony compound in terms of antimony element and (E) 0.1-10 pts.wt. of a compound of formula I (D is bivalent organic group; k is 0 or 1; X is bivalent organic group to form 5- or 6-membered ring of formula II). Polyethylene terephthalate is used as the thermoplastic polyester of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame-retardant resin composition, and more particularly to a flame-retardant polyester resin composition with excellent thermal stability.

[Prior art and its problems] Thermoplastic polyesters represented by polyethylene terephthalate and polybutylene terephthalate have excellent chemical and mechanical properties, and therefore have a rating of 11i1. film,
It is widely used as plastics, etc., but in recent years, it has been particularly used in the plastic field to be molded into electrical equipment parts, automobile interior and exterior parts, and other molded products using injection molding machines.
started to be used in large quantities.

On the other hand, the physical properties of thermoplastic polyester can be further improved by adding various additives such as male reinforcing materials such as glass fibers and carbon fibers, and function-imparting agents such as inorganic fillers. Expanded as above.

However, in recent years, the shapes required for these molded products have become more complex, thinner, and smaller than ever before, reflecting social trends such as higher functionality, lighter weight, and resource conservation. It's across the street.

Therefore, for thermoplastic polyester as a molding material, excellent fluidity within the molding mold is considered to be one of the four essential material properties.

It has been known that the melt fluidity of a thermoplastic polyester largely depends on its molecule m, and that the smaller the molecular weight, the greater the plug fluidity.

Therefore, as a thermoplastic polyester with excellent fluidity, one with a small molecular weight can be used as a molding material.
On the other hand, it is known that the n-region strength of the molded product, as well as the so-called toughness such as tensile elongation and bending deflection, also depend on the intermolecularity of the thermoplastic polyester, and that the lower the molecular weight of the polyester, the lower the toughness. There is. This means that if thermoplastic polynisful with small molecules is used to improve the fluidity of the molding material, it will inevitably result in molded products with low toughness and strength.
Particularly when it is necessary to improve fluidity in order to cope with the thinning of the molded product, the decrease in strength due to the thinning of the wall and the decrease in strength due to the decrease in molecular weight may combine to reduce the amount of 1q before it can be used in actual use. There are many.

In order to improve the strength of molded products, for example, alpha-olenoin and alpha, beta unsaturated carboxylic acid salts are added to thermoplastic polyester (Japanese Patent Publication No. 45-26225).

Rubbers such as copolymers of acrylic acid esters and ethylene (Japanese Patent Publication No. 45-38908), polyacrylic acid aliphatic esters (Japanese Patent Publication No. 45-38909), or butyl rubber (Japanese Patent Publication No. 46-5224) The method of adding trade polymers, and the method of adding boxy compounds (Tokukosho/18-
6175, Japanese Patent Publication No. 47-13860, Japanese Patent Publication No. 47-2193) are known.

However, all of these methods tend to impair the fluidity of the thermoplastic ↑1 polyester, and their application to thin-walled molded products is subject to substantial restrictions.

However, in response to this, it has been proposed that the fluidity during molding can be improved without impairing the toughness and strength of the molded product by blending a specific polycaprolactic derivative into thermoplastic polyester. There is.

By the way, thermoplastic polyester is inherently flammable.
- Once ignited, it will not extinguish and burn gradually even if the fire source is removed, so its application is limited, and it has become a serious defect from a fire safety perspective, especially in the field of electrical and communication equipment. There is.

For this reason, many attempts have been made to make thermoplastic polyester flame retardant. As one of the countermeasures against this problem, it is known and put into practical use to mix and use an organic halogen compound as a flame retardant and an antimony compound as a flame retardant aid.

However, when this flame retardant technology is applied to thermoplastic polyester compositions containing the aforementioned polycaprolactone derivatives, the melt thermal stability of the thermoplastic polyester is impaired, resulting in poor properties of the resulting molded articles, especially mechanical strength. A new problem arises in that stable molding is difficult. periodic table 1 such as sodium antimonate as f1 combustion aid. When antimony 11, a metal of groups II and II, is used, the melt thermal stability of thermoplastic polynisder is improved to some extent compared to when other antimony compounds, such as antimony trioxide, are used, but it is not always sufficient. do not have.

[Object of the Invention] As a result of intensive studies to solve the various problems mentioned above, the present inventors have added a specific oxazoline compound to a thermoplastic polyester composition containing a polycaprolactone derivative, an organic halide, and an antimony compound. The present invention was achieved based on the finding that when blended in a specific amount, an excellent flame retardant effect can be imparted without impairing the melt thermal stability and melt fluidity of the thermoplastic polyester.

[Configuration and Effects of the Invention] The present invention provides (A) per 100 weight of thermoplastic polyester, (B) end-blocked polycaprolactone with a width of 0.1 to 30, and (C) organic halide with a halogen element ω of 0. .1 to 30 parts by weight, (D) 0.61 to 20 parts by weight of an antimony compound as an antimony element foot, and ([) 0.1 to 10 parts by weight of a compound represented by the following general formula [I]. This is a flame-retardant resin composition.

The present invention will be explained.

The thermoplastic polyester as component (A) used in the present invention uses terephthalic acid or its ester-forming derivative as the acid component, and has 2 to 2 carbon atoms as the glycol component.
The main target is a linear saturated polyester obtained using glycol or an ester-forming derivative thereof,
For example, polyethylene terephthalate, polypropylene terephthalate 1, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate 1~, polycyclohexane-1,4-dimethylol terephthalate, polyneopendyl terephthalate~ polyethylene-2,6-naphthalate, polytetramethylene-2,6-naphthalate, polyhexamethylene-
Examples include 2,6-naphthalate, polyethylene-2,7-naphthalate, polytetramethylene-2,7-naphthalate, polyhexamethylene-2-naphthalate, and polyethylene-1,5-naphthalate-1. Among these, polyethylene terephthalate is particularly preferred.

These thermoplastic polyesters may be used in combination or in a mixed composition of two or more.

Other polyesters may also be used, such as those in which part of the terephthalic acid component or the glycol component having 2 to 10 carbon atoms is replaced with another copolymer component as the acid component.

Such copolymerization components include, for example, isophthalic acid and phthalic acid; halogen M-substituted phthalic acids such as tetrabromophthalic acid and tetrabromoterephthalic acid; al-substituted phthalic acids such as methyl terephthalic acid and methyl isophthalic acid;
Naphthalene dicarboxylic acids such as 2°6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid; diphenyl dicarboxylic acids such as 4,4-diphenyl dicarboxylic acid and 3,4°-diphenyl dicarboxylic acid; ; Aromatic dicarboxylic acids such as 4,4-diphenoxyethane dicarboxylic acid; succinic acid, adipic acid, sebacic acid, azelaic acid, decadicarboxylic acid,
Aliphatic or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, 1,4-
Aliphatic diols such as cyclohexane dimetatool, etc.; dihydroxybenzenes such as hydroquinone, resorcinol, etc.; hysphenols such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, etc.: Aromatic diols such as ether diols obtained from hisphenols and glycols such as ethylene glycol; polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, etc.; ε-oxy Examples include oxycarboxylic acids such as caproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid, and the like. One or more of these copolymerization components can be used, and the proportion thereof is 20 mol% or less, especially 10 mol% or less, based on the total dicarboxylic acid (half of the amount of oxycarboxylic acid is calculated as carboxylic acid). It is preferable that

Furthermore, these thermoplastic polyesters contain branching components such as tricarballylic acid, trimellisic acid, 1 to limerite 1
Acids capable of forming trifunctional or tetrafunctional esters such as -trifunctional or pyromolic acids, and trifunctional or ( Alcohol having the ability to form a tetrafunctional ester is added to 1.0% or less, preferably 0%.
．． 5 mol% or less, preferably 0.3 mol% or less, may be copolymerized. using 35
When measured at °C, 0.35 or more, and even 0.45
In particular, it is preferably 0.50 or more.

The above-mentioned thermoplastic polyester can be produced by a conventional production method, such as a melt polymerization reaction or a method combining this with a solid state polymerization reaction.

The end-capped polycaprolactone used in the present invention as component (B) has a number average molecular weight of 600 or more.
It means polycaprolactone in which at least 50% of the total terminal groups (0 or less) are capped with a capping agent [hereinafter referred to as end-capped polycaprolactone]. When this end-blocked polycaprolactone is blended in an appropriate amount with a thermoplastic polyester, it can improve the molding fluidity and also exhibit the effect of greatly improving the so-called toughness and strength of the molded product, such as tensile elongation and bending flexibility.

The end-capped polycaprolactone is prepared by a known method to
- It can be produced by reacting polycaprolactone having a free carboxyl group and/or hydroxyl group at the end obtained by ring-opening polymerization of caprolactone with a monovalent compound that reacts with the carboxyl group or M% of water. can.

Examples of the polymerization initiator used in the ring-opening polymerization of ε-caprolactone include monohydric alcohols such as N-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, lauryl alcohol, and myristyl alcohol; Ethylene glycol, propylene glycol, ethyl ethylene glycol, 2-methyl-1,2-panediol, pinocol, β-butylene glycol, diethylene glycol, tetramethylene glycol, neopentyl glycol, 1,4 cyclohexane dimetatool Glycols such as glycerin, 1,2.3-butane] diol, 1,2.3
- Trihydric alcohols such as pentantriol; Tetrahydric alcohols such as erythritol and pentaerythritol; Monovalent carboxylic acids such as benzoic acid, p-methylbenzoic acid, lauric acid, myridic acid; such as isophthalic acid and phthalic acid. , terephthalic acid, 2,6-naphthalene dicarboxylic acid, 44'-diphenoxyethane dicarboxylic acid,
Divalent carboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, decadicarboxylic acid, and cyclohexynedicarboxylic acid; for example, trivalent carboxylic acids such as tricarbaryl I, limericic acid, and trimellitic acid; for example, pyromellitic acid Examples include oxycarboxylic acids such as ε-oxycarboxylic acid and hydroxyethoxybenzoic acid. Furthermore, as a catalyst for accelerating the ring-opening polymerization reaction of ε-caprolactone using these polymerization initiators, tin-based catalysts such as tetraoctyltin, diphenyltin, and dilaurate, which are known ring-opening catalysts, may be used. It is preferable to use a titanium-based catalyst such as or tetrabutyl titanate.

The type of terminal group of polycaprolactone obtained in this way varies depending on the type of polymerization initiator used; alcohols have hydroxyl groups, carboxylic acids have carboxyl groups, and oxycarboxylic acids and water have both hydroxyl and carboxyl groups. becomes the terminal group. Among these, those using glycols as a polymerization initiator are preferred.

These polycaprolactones must have at least 50%, preferably 70% or more of their total end groups blocked. Ideally, all terminal groups of polycaprolactone are capped, and this is particularly preferred. For this blocking, any monovalent compound can be used as long as it eliminates the activity of the terminal carboxyl group or terminal hydroxyl group of polycaprolactone. For example, ester bonds, ether bonds, urethane bonds, amide bonds, etc. are used for blocking, but blocking by ester bonds is preferred. Compounds used for blocking with ester bonds include, for example, monovalent carboxylic acids or ester-forming derivatives thereof when the terminal group is a hydroxyl group, and monovalent alcohols when the terminal group is a carboxyl group. or its ester-forming derivatives. Examples of the monovalent carboxylic acids or ester-forming derivatives thereof include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, laufonic acid, myristic acid, benzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, 2,3,4.5- Examples include carboxylic acids such as tetramethylbenzoic acid, their acid anhydrides, acid halides, etc., and ester derivatives of these carboxylic acids, such as phenyl acetate, ethyl benzoate, methyl benzoate, ethyl toluate, etc. can be mentioned. Examples of monohydric alcohols or their ester-forming derivatives include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, n-amyl alcohol, and lauryl alcohol, and their halocarbonate esters. and carboxylic acid esters.

Polycaprolactone whose terminals are blocked by the reaction of polycaprolactone with a monohydric alcohol or its ester-forming derivative, or a monovalent carboxylic acid or its ester-forming derivative can be prepared by using a known esterification reaction. can be easily obtained.

Particularly preferred of the end-capped polycaprolactones is polycaprolactone represented by the general formula % ] [ ]. In the above general formula, when R11 is glycol, m.

is O, m is 2, and R12C〇- represents the residue of the monovalent carboxylic acid used for blocking. In addition, when R11 is a dicarboxylic acid, m becomes O, mo becomes 2, and =
〇R12 represents the residue of the monohydric alcohol used for blocking. Furthermore, when R11 is an oxycarboxylic acid,...
, lll° is 1, and R12C〇- is 1 used for blockade.
The residue of the carboxylic acid, O R 13, represents the residue of the monohydric alcohol used for blocking.

By blending 1q end-blocked polycaprolactone into thermoplastic polyester in this way, it is possible to significantly improve molding fluidity and toughness, but these effects greatly depend on the molecular weight of the end-blocked polycaprolactone. If the number average molecular weight is larger than 20.000, these effects, especially the improvement of toughness and strength, will not be achieved at all or if the number average molecular weight is smaller than 600, the volatility will be high and the thermal stability will be high. This is not desirable for practical purposes. Therefore, in the present invention, the end-blocked polycaprolactone has a number average molecular weight of 600 or more, 20,
000 or less, preferably 700 or more and 10,000 or less,
It is more preferably 700 or more and 5,000 or less, and even more preferably 700 or more and 2,000 or less.

In the present invention, the amount of end-blocked polycaprolactone as component (B) added is 0 per 100 weight of thermoplastic polyester.
．． It is 1 to 30 parts by weight. If this amount is less than 0.1 part by weight, the effect of addition will not be sufficient, and if it is more than 30 parts by weight, the effect will be saturated. This is not desirable as the characteristics of A more preferable addition period is 1 to 15 parts of camellia.

The organic halogen compound used as component (C) in the present invention has a chlorine atom or a bromine atom in the molecule and acts as a flame retardant for thermoplastic polyester, and is a well-known organic halogen compound commonly used as a flame retardant. Compounds included.

Such compounds include, for example, hexabromobenzene,
Hexachlorobenzene, pentabromo-1-luene, pentachlorotoluene, pentabromophenol, pentachlorophenol, hexyl-promobiphenyl, decabromohyphenyl, tel-labmobutane, hexabromocyclododecane, baku-propentacyclodecane, deca Bromodiphenyl ether, octabromodiphenyl ether.

Organic halogen compounds for small molecules such as hexabromodiphenyl ether, ethylene bis(tetrabromophthalimide), tetrachlorobisphenol-A, and tetrabromobisphenol-A, halogenated polycarbonates (manufactured using brominated hisphenol-A as a raw material, for example) polycarbonate oligomers), halogenated epoxy compounds (for example, jepoxy compounds produced by the reaction of brominated bisphenol-A and epichlorohydrin, and monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin), polychlorostyrene,
Examples include halogenated polymers and oligomers such as brominated polystyrene, poly(dibromophenylene oxide), dechlorane plus (condensation compound of 2 moles of tetrachlorocyclopentadiene and 1 mole of cyclooctadiene), or mixtures thereof. can.

The amount of these organic halogen compounds added is 0.1 to 0.1 to 100% by weight of the thermoplastic polyester.
The amount is 30 parts by weight, preferably 1 to 15 parts by weight. 0.1
If the amount is less than the layered portion, the flame retardance will not be sufficient, and if it exceeds 30 parts by weight, the physical properties of the composition will deteriorate significantly.

In the present invention, the antimony compound used as component (D) functions as a flame retardant auxiliary agent that promotes the flame retardancy of the organic halogen compound as component (C). Typical examples include antimony trioxide, antimony chloride, and periodic table 1. Examples of antimonates include antimonates of metals of Group II and II, and further examples of antimonates include antimonates of sodium, potassium, zinc or nickel, and mixtures thereof.

Thermoplastic polyester 10 during addition of antimony compound
The amount of antimony element in the antimonate is 0.1 to 20 parts per 0 mm part, preferably 1 to 15 parts. If this amount is less than 0.1 parts by weight, the effect as a flame retardant aid will not be sufficiently expressed.

Moreover, when the amount is more than 20 parts by weight, the flame retardant effect is saturated, and 2
Not only does the effect not increase compared to when 0 parts by weight is added, but the properties of the resin composition further deteriorate by 1q, which is not preferable.

Component (E) used in the present invention is represented by the following general formula [I] as described above.

-10 alkyl group, C6-12 aryl group.

Examples include a cycloalkyl group having 5 to 12 carbon atoms, and an aralkyl group having 8 to 20 carbon atoms.

More specifically, the alkyl group is methyl.

ethyl, propyl, butyl, pentyl, hexamethyl,
Octamethyl, nonamethyl, decamethyl.

Examples include dimethylmethyl, and aryl groups include phenyl, naphthyl, and diphenyl.

It is a compound called bisoxazoline, which has 6
The circular ring is a compound called bisoxazine.

Preferred examples of the organic group of ,-C
H2-, -CH2・C)+2--C(CH3>2
-, etc.), and the cycloalkyl group is cyclohexyl. Among these, as X, ethylene and trimethylene are particularly preferable. D in the general formula [I] is a divalent organic group, and this group is, for example, a fullkylene group having 1 to 10 carbon atoms.

Examples include an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms.

More specifically, the alkylene group includes methylene, ethylene, propylene, butylene, pentylene, hexamethylene, octamethylene, nonamethylene, decamethylene,
Examples include dimethylmethylene, and the arylene group is phenylene.

Naphthylene, diphenylene, 5R' -+5 (where R
゛ is -o-, -co-, -5-3OZ-, -CH2-,
-CH2CH2-.

C(CH2)2-, etc.), and the cycloalkylene group is cyclohexylene.

Further, k in the general formula [I] is O or 1, and among these, O is preferable.

Specific examples of the compound represented by the general formula [I] include the following compounds.

2.2゛-bis(2-oxazoline), 2,2°-bis(4-methyl-2-oxazoline), 2,2°-bis(
4,4-dimethyl-2-oxazoline), 2.2-
Bis(4-ethyl-2-oxazoline), 2.2bis(
44-diethyl-2-oxazoline), 22"-bis(
4-propyl-2-oxazoline).

2.2'-bis(4-butyl-2-oxazoline).

2.2-bis(4-hexyl-2-oxazoline).

? , 2°-bis(4-phenyl-2-oxazoline).

2.2′-bis(4-cyclohexyl-2-oxazoline), 2,2°-bis(4-benzyl-2-oxazoline), 2.2′-p-phenylenebis(2-oxazoline), 2 , 2°-m-phenylenebis(2-oxazoline), 2.2'-〇-phenylenebis(2-oxazoline), 2.2'-p-phenylenebis(4methyl-2-oxazoline), 2 , 2°-p-phenylenebis(4,4-dimethyl-2-oxazoline), 2.2'
-m-phenylenebis(4-methyl-2-oxazoline), 2,2°-m-phenylenedos(44-dimethyl-
2-oxazoline), 2,2'-ethylenebis(2
-oxazoline), 2.2°-tetramethylenebis(2
-oxazoline), 2,2'-hexamethylenebis(2
-oxazoline), 2,2-octamethylenebis(2-
oxazoline), 2,2"-decamethylenebis(2
-oxazoline), 2,2'-ethylenebis(4-
methyl-2-oxazoline).

22°-te]ramethylenebis(4,4-dimethyl-2
-oxazoline), 2,2'-9,9'-diphenoxyethanebis(2-oxazoline), 2,2°-cyclohexylenebis(2-oxazoline), 2,2°-diphenylenebis(2-oxazoline) ); bisoxazoline compounds such as 2,2°-bis(5,6-sihydro 4H
-1,3-oxazine), 2,2°-methylenebis(5
,6-sihydro4l-(-1,3-oxazine).

2.2°-ethylenebis(5,6-sihydro4H-1
3-oxazine), 2,2°-propylene bis(5,6
-Sihydro 48-1,3-oxazine), 2,2゜butylenebis(5,6-Sihydro 4l-(-1,3-oxazine), 2,2'-hexamethylenebis(5,
6-dihydro-4@-1,3-oxazine), 2.2-
p-phenylenebis(5,6-sihydro4H-i, 3-
oxazine), 2,2"-m-phenylenebis(5゜6
-Sihydro 41-1-1,3-oxazine), 2
．． 2'-naphthylene bis(5,6-sihydro41-1
-1,3-oxazine), 2,2°-p,p'-diphenylenebis(5,6-sihydro4l-(-1,3-oxazine), etc.).

Among these compounds, 2,2°-bis(2oxazoline) and 2,2°-m-phenylenebis(2oxazoline) are particularly preferred. These compounds can be easily synthesized by a method of ring-closing the corresponding bisamide alcohol by treating it with a dehydrating agent such as a-sulfuric acid or thionyl chloride, or by a method of ring-closing the corresponding bisamide halide by treating it with an alkali. The method is not limited, and other methods can be used as appropriate.

The compounding amount of these compounds represented by the above general formula [I] is 0.1 to 100 parts by weight of the thermoplastic polyester.
It requires a hanging weight of 10 times, preferably 0.3 to 3 times. If the blending distance is less than 0.1, the effects of the present invention will not be achieved and there will be no practical meaning. On the other hand, even if the amount exceeds 10 parts, not only is no increase in the effect expected, but also a gel-like substance is formed, which is thought to be partially due to crosslinking of the thermoplastic polyester, and the molten resin during molding. Liquidity is impaired.

The flame-retardant resin composition of the present invention may further contain various additives for the purpose of improving other properties.

For example, fibrous materials such as glass fiber, asbestos, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, steel m fiber, ceramic fiber, boron whisker fiber, etc. are used as fillers to improve mechanical strength and heat resistance. , mica, silica, tar, calcium carbonate, glass peas, glass peaks, clay, and wollastonite.

These fillers are usually blended as surface modifiers for the reinforcing material 1 or for the purpose of modifying electrical, thermal, and other properties, but among these fillers, especially when using glass fiber, mechanical strength It exhibits a number of features such as greatly improved heat resistance and reduced mold shrinkage.

There are no particular limitations on the glass fibers, as long as they can be used for reinforcing resins in general, and can be applied to the composition of the present invention. For example, Cho I! The fiber type (glass roving), short fiber-like chopped toss 1 to land, milled fiber, etc. can be selected and used. Glass fiber is also used as a sizing agent (
For example, polyvinyl acetate, polyester sizing agents, etc.), coupling agents (for example, silane compounds, borane compounds, etc.),
It may also be treated with other surface treatment agents. Furthermore, it may be coated with a resin such as a thermoplastic resin or a thermosetting resin. Normally, long fiber type glass fibers are cut into desired lengths before or after blending with resin, but
This mode of use is also included in the present invention.

Additionally, inorganic substances such as carbonates of alkaline earth metals (eg, calcium carbonate) can be used as nucleating agents to promote crystallization during molding and improve molding cycles.

magnesium carbonate, etc.), sulfates (e.g., calcium sulfate, etc.), metal oxides such as titanium oxide, aluminum oxide, zinc oxide, etc., talc, graphite, aluminum silicate, clay, metal salts of organic acids (e.g., stearate,
benzoate, salicylate, tartrate, montanate,
terephthalates, etc.), alkaline earth metals or metal glycolates of titanium, germanium, antimony, tungsten, manganese; ionic copolymers consisting of α-olefins and α,β-unsaturated carboxylates, Can be added for valve use.

Further, flame retardants other than organic halogen compounds, such as red phosphorus and phosphorus compounds such as phosphonic acid amide, can also be added.

Furthermore, for the purpose of improving heat resistance, antioxidants such as hindered phenol compounds and sulfur compounds, or heat stabilizers such as phosphorus compounds may be added. In particular, the phosphorus compound added for this purpose is represented by the following general formula (i
], Compounds represented by (ii) are desirable.

[However, in the formula, X, Y, and Z are each a hydrogen atom, and the monovalent hydrocarbon group in the above formula is preferably an alkyl group, an aralkyl group, an aryl group, etc. having 12 or less carbon atoms. Methyl and ethyl are the alkyl groups.

Examples include propyl, isopropyl 2-butyl, pentyl, hexyl, cyclohexyl, ocdyl, decyl, etc., and examples of the aryl group include phenyl, naphthyl, methylphenyl, phenyl phenyl, brominated phenyl, etc. Furthermore, benzyl is exemplified as aralkyl. Specific examples of phosphorus compounds include phosphoric acid and trimethyl phosphate.

Phosphate esters such as methyl diethyl phosphate, tonoethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate; phosphorous acid, trimethyl phosphite, triethyl phosphite, j-phosphite Draft phosphate esters such as liphenyl; phosphonic acids such as phosphonic acid, phenylphosphonic acid, and phenyl phenylphosphonate; and derivatives thereof; phosphinic acid, phenyl phosphonate;
Examples include sphinic acids and derivatives thereof (such as sphinic acid and dimedylphosnoic acid). Among these, trimethyl phosphate is particularly desirable.

It is a (sub)phosphoric acid ester such as triphenyl (sub)phosphate. These phosphorus compounds can be used alone or in combination of two or more.

Furthermore, various epoxy compounds may be added for purposes such as improving hydrolysis resistance. As for epoxy compound,
One example is bisphenol A epoxy compounds obtained by reacting bisphenol A and epichlorohydrin, aliphatic glycidyl ethers obtained by reacting various glycols or glycerol with evichlorohydrin, novolak epoxy compounds obtained from novolac resins and epichlorohydrin, and alicyclic epoxy compounds. Preferably, alicyclic compound type epoxy compounds are preferred, and particularly preferred epoxy compounds include bisphenol A type epoxy compounds, diglycidyl ethers of low molecular weight polyethylene glycol, and diglycidyl esters of aromatic dicarboxylic acids.

Other additives include ultraviolet absorber 1 colorant.

Examples include lubricants, antistatic agents, foaming agents, and the like.

Also, in small proportions, other thermoplastic resins such as sterol resins, acrylic resins, polyethylene, polypropylene,
Fluororesin, polyamide resin, polycarbonate resin,
Polysulfone, etc.; thermosetting resins such as phenolic resins,
Melamine resins, unsaturated polyester resins, silicone resins, etc.; and soft thermoplastic resins such as ethylene-vinyl acetate copolymers, polyester elastomers, etc. may also be added.

Any method of formulation can be used to formulate the flame retardant resin compositions of the present invention. Normally, it is preferable to disperse these ingredients more uniformly, and all or part of them can be mixed simultaneously or separately, for example, in a Blesseder 2 Kneader,
A method of mixing and homogenizing using a mixer such as a roll or an extruder, or a method of mixing some of the mixed components simultaneously or separately using a blender, a roll, an extruder, etc., and then adding the remaining components. , a method of mixing and homogenizing using these mixers or extruders can be used.

The most common method is to homogenize a pre-triblended composition by melt-kneading it in a heated extruder.
This is a method of extruding it into a wire shape, then cutting it to a desired length and granulating it. The composition thus prepared is usually sufficiently dried and kept in a dry state before being charged into a molding machine hopper and subjected to molding. Other methods include, for example, a method in which other components are added or mixed during the production of the thermoplastic polyester, before the polycondensation, after the polycondensation, or during the polycondensation.

In particular, when glass fiber is used as a filler, it is melt-kneaded together with other ingredients in an extruder in order to prevent its crushing as much as possible during kneading and to improve workability during composition production. For example, glass fiber-free polyester resin granules produced in an extruder may be mixed with various amounts of glass chopped strands or a pre-prepared glass fiber-rich thermoplastic resin. The resulting composition can also be charged into a molding machine hopper and subjected to molding.

The flame-retardant resin composition of the present invention can be easily molded by a conventional method using a general thermoplastic resin molding machine.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples. In addition, the intrinsic viscosity of the thermoplastic polyester described in the examples is a value measured at 35° C. in an orthochlorophenol solution. Furthermore, parts refer to parts by weight.

Various properties in the examples were measured by the following methods.

(1) Static strength: Tensile test: Based on ASTHD-638.

(2) Melt fluidity and melt thermal stability: Temperature 28 with Koka type flow tester (manufactured by Shimabara Seisakusho)
0℃, load 1100K(]/Cm2, nozzle L/D=
Melt viscosity (poi) under the condition of 10/1 (mm/mm)
se) was measured. Note that the residence time was defined as the time from when the resin melted until the measurement was performed, and the melting thermal stability was evaluated based on the degree of change in residence time between 5 minutes and 15 minutes.

(3) Flammability: Conforms to the American Underwriters Laboratories standard tNabjiect 94 (Kano-94).

As a test piece, length 5゛° x width 1/2° x thickness 1/32''
It was molded by injection molding method and used.

Examples 1 to 2 and Comparative Examples 1 to 4 Glass chopped strands with a fiber length of 3 mm (manufactured by Nippon Electric Glass VTJ), brominated polystyrene ( [Pyrocheck 68-PB manufactured by J Nissan Ferro Organic Chemical ■), antimony trioxide (``Patox C'' manufactured by Nippon Seiko ■) or sodium antimonate (1''S8-AJ manufactured by Nippon Seiko ■) as an antimony compound, crystals Ionomer (Himilan 1707J Mitsui DuPont Polychemicals) as a nucleating agent, end-capped polycaprolactone as a plasticizer, triphenyl phosphate and 1,3-phenylenebis-2-oxazoline (manufactured by Sotoen Yakuhin Kogyo) as a stabilizer. were added in the proportions shown in Table 1, respectively, and mixed uniformly using a V-type blender.

The resulting mixture was melt-mixed in a single-screw extruder with a diameter of 68 mm at a barrel temperature of 280° C., and the thread discharged from the die was cooled and cut to obtain a pellet for molding.

Next, the pellets were dried with hot air at 140°C for 5 hours, and then a test piece mold for measuring physical properties was attached to a 5-ounce indexing machine, and the cylinder temperature was set at 260'C.

A test piece was molded under the molding conditions of a mold temperature of 80° C., an injection pressure of 800 Kg/cm 2 , a cooling time of 20 seconds, and a total cycle time of 35 seconds.

The properties of the molded article thus obtained are shown in Table-1.

The end-blocked polycaprolactone used here is a commercially available polycaprolactone whose terminal group is a hydroxyl group (Daicel ■: trade name Plaxel 11212, number average molecular weight 1200>100 parts, 80 parts of methyl benzoate and 0.002 parts of tributyl titanate). 190~
The reaction mixture was heated to 210° C. and stirred for 10 hours while removing methanol distilled from the reaction system, followed by removing excess methyl benzoate under reduced pressure. The hydroxyl value of this end-capped polycaprolactone is J
The value measured in accordance with IS-1557 was 1.7.

Thermoplastic polyesters such as polyethylene terephthalate can be made flame retardant with brominated polystyrene and antimony compounds and have a flammability rank of U [v-O of 94].
However, it was difficult to produce 1 q of good molded products due to the poor melt flowability of the resin during molding (Comparative Example 1).

By blending the end-capped polycaprolactone into the composition, the melt fluidity can be significantly improved, but the melt thermal stability, i.e., i? i! Station 5
There is a large change in melt viscosity from the melt viscosity at 15 minutes of residence to that at 15 minutes of residence (Comparative Example 2). By using sodium antimonate instead of antimony trioxide as the antimony compound, this decrease in melt viscosity can be suppressed to some extent (Comparative Example 3), but it cannot be said to be preferable for stable molding.

However, by further adding 1,3-phenylenebis-2-oxazoline to these compositions, their thermal stability during melting is greatly improved while maintaining their good melt flow properties, which is due to the fact that the antimony compound Effects were expressed in both antimony trioxide and sodium antimonate (Examples 1 and 2).

When this 1,3-phenylenebis-2-oxazoline is added without end-blocking polycaprolactone, its fluidity is suppressed from decreasing in melt viscosity due to retention, but the melt viscosity is not suitable for injection molding. (Comparative Example 4) Both effects are expressed for the first time when flame-retardant thermoplastic polyester is used in combination with end-blocked polycaprolactone. We were able to produce a flame-resistant thermoplastic polyester resin composition with excellent heat resistance.

Claims (1)

[Claims] 1. (A) per 100 weight of thermoplastic polyester, (B
) 0.1 to 30 parts by weight of end-capped polycaprolactone, (C) organic halide as halogen element amount 0.1
~30 parts by weight, (D) antimony compound as antimony element amount 0.
1 to 20 parts by weight, and (E) a compound represented by the following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... [I] [However, D in the formula is a divalent organic group, k is 0 or 1. In addition, X is a divalent organic group, and the ring structure ▲ has numerical formulas, chemical formulas, tables, etc. ▼ is a group that forms a 5-membered ring or a 6-membered ring. ] A flame-retardant resin composition containing 0.1 to 10 parts by weight. 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic polyester is polyethylene terephthalate. 3. End-capped polycaprolactone has the general formula [II] [R^
1^2CO■O-■CH_2■_5CO■_nO■_m
-R^1^1■CO■O■CH_2■_5CO■_n-
OR^1^3■_m'...[II] However, in the formula, R^1^1 is an (m+m')-valent organic group, R^
1^2 and R^1^3 are each a monovalent organic group, n, n'
are each a number of 2 or more, m and m' are each a number of 0 to 4, and (m+m') is 1 or more. The flame-retardant resin composition according to claim 1, which is an end-capped polycaprolactone represented by the following formula and having a number average molecular weight of 600 or more and 20,000 or less. 4.Claim 1, wherein the halogen of the organic halide is bromine.
The flame-retardant resin composition described in . 5. The flame-retardant resin composition according to claim 1, wherein the organic halide is brominated polystyrene. 6. The flame-retardant resin composition according to claim 1, wherein the antimony compound is antimony trioxide. 7. The flame-retardant resin composition according to claim 1, wherein the antimony compound is an antimonate of a metal of Group I, II or VIII of the Periodic Table. 8. The flame-retardant resin composition according to claim 7, wherein the antimony compound is sodium antimonate.