JPH1025401A - Flame-retardant polyester elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of forming a flame-retardant polyester elastomer which is excellent in all of flame retardancy, mechanical properties, heat resistance, and hydrolytic resistance, is reduced in volatilization during heating, and does not contain any flame retardant. SOLUTION: The composition comprises (A) 100 pts.wt. thermoplastic polyester elastomer and (B) 0.5-50 pts.wt. compound having a triazine group. The elastomer (A) is obtained from 100 pts.wt. block copolyester (a1 ) obtained by reacting a crystalline aromatic polyester with a lactone and 0.1-10 pts.wt. compound (a2 ) which has two or more functional groups reactive with the terminal groups of the copolyester (a1 ) and which, when heated at 200 deg.C for 30min, has a heating loss ratio defined by (W1-W2)/W1 of 0.1 or lower. In the relationship, W1 and W2 are the weights of the compound (a2 ) before and after the heating, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant polyester elastomer composition using a non-halogen flame retardant. More specifically, it relates to a flame-retardant polyester elastomer composition having excellent mechanical properties, low volatility upon heating, and excellent heat resistance and hydrolysis resistance.

[0002]

2. Description of the Related Art A thermoplastic polyester type block copolymer obtained by the reaction of an aromatic polyester and a lactone as a resin having rubber-like elasticity and useful as a molding material for fibers, films and various molded articles. Is commonly used. As a method for producing such a copolymer, there is the following method.

[0003] For example, Japanese Patent Publication No. 48-4116 discloses a method of reacting a crystalline aromatic polyester with a lactone.

Japanese Patent Publication No. 48-4115 discloses a method in which a crystalline aromatic polyester is reacted with a lactone, and the resulting block initial copolymer is reacted with a polyfunctional acylating agent to extend the chain. ing.

[0005] JP-B-52-49037 describes a method of polymerizing lactones in the solid state in the presence of a crystalline aromatic polyester.

The polyester type block copolymer obtained by these methods has excellent rubber-like elasticity and also has excellent weather resistance. However, these compositions have insufficient heat resistance, and have the disadvantage that when exposed to a high temperature for a long time, the strength and the elongation are significantly reduced. In addition, these polymers have poor hydrolysis resistance and are prone to hydrolysis in the presence of water. Therefore, it is difficult to use these compositions as they are as raw materials such as fibers, films, and molding materials.

In order to improve the heat resistance and hydrolysis resistance of such a polyester type block copolymer, a method of blending an epoxy compound having one or more functionalities (Japanese Patent Laid-Open No. 58-162654) has been proposed. Proposed.

By this method, the ripening resistance and hydrolysis resistance of the above composition are improved. However, this method has a problem that a large amount of unreacted epoxy monomer volatilizes when the obtained composition is heated depending on the type of epoxy used.

Further, as a general method for imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based flame retardant as a flame retardant into the thermoplastic resin has been used.

However, in such a method, a part of the halogen-based flame retardant is decomposed at the time of kneading and molding, and free halogen gas and / or a halogen compound are generated.
These gases and / or halogen compounds corrode the surfaces of cylinders, screws, and molds of compounding kneaders, injection molding machines and the like. Furthermore, in the field of electric equipment parts and electronic equipment parts, these halogen gases and / or halogen compounds may corrode metal parts, resulting in poor contact and poor conduction.

Further, in order to enhance the flame retardancy, an antimony compound is usually often used in combination as a flame retardant auxiliary. However, since the antimony compound is a foreign substance for the thermoplastic resin, there is a disadvantage that mechanical properties such as strength and elongation are reduced.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent flame retardancy, mechanical properties, heat resistance, and hydrolysis resistance, low volatility during heating, and low halogen content. An object of the present invention is to provide a flame-retardant polyester elastomer composition containing no flame retardant.

[0013]

The first flame-retardant polyester elastomer composition of the present invention comprises (A) 100 parts by weight of a thermoplastic polyester elastomer and (B) 0.5 parts by weight of a compound having a triazine group. 50 parts by weight, comprising a flame-retardant polyester elastomer composition,
This thermoplastic elastomer (A) comprises: (a ₁ ) 100 parts by weight of a polyester type block copolymer obtained by reacting (i) a crystalline aromatic polyester with (ii) a lactone; and (a ₂ ) 2 A compound having a functionality of 3 or more at 200 ° C.
A compound capable of reacting with the terminal group of the polyester-type block copolymer (a ₁ ) has a heat loss ratio represented by the following formula (I) of 0.1 or less when subjected to heat treatment for 0 minutes, and Formed from 0.1 parts to 100 parts by weight:

[0014]

(Equation 3)

Here, W1 and W2 are the weights of the bifunctional compound before and after the heat treatment, respectively.

The second flame-retardant polyester elastomer composition of the present invention comprises (A) 100 parts by weight of a thermoplastic polyester elastomer and (B) 0.5 to 50 parts by weight of a compound having a triazine group. to a flame-retardant polyester elastomer composition, the thermoplastic elastomer (a) is, (a ₁₎ (i) crystalline aromatic polyester and (ii) a polyester type block copolymer obtained by reacting a lactone 100 parts by weight of a polymer, (a ₂ ) a compound having two or more functions,
A compound capable of reacting with the terminal group of the polyester-type block copolymer (a ₁ ) has a heat loss ratio represented by the following formula (I) of 0.1 or less when subjected to heat treatment for 0 minutes, and 0.1 part by weight to 100 parts by weight, and (a ₃ ) a monofunctional compound 10 having a functional group capable of reacting with a terminal group of the polyester type block copolymer (a ₁ ) 10
Formed from the following parts by weight:

[0017]

(Equation 4)

Here, W1 and W2 are the weights of the bifunctional compound before and after the heat treatment, respectively.

In a preferred embodiment, the compound (B) having a triazine group is melamine and / or melamine cyanurate.

In a preferred embodiment, the compound (B) having a triazine group is melamine cyanurate in a powder form, and the image of the powder taken by a scanning electron microscope (SEM) is analyzed by an image analyzer. Has an average particle diameter of 2 μm to 100 μm.

In a preferred embodiment, the bifunctional or higher-functional compound (a ₂ ) is selected from the group consisting of bisphenol F-diglycidyl ether, bisphenol A-diglycidyl ether, and bisphenol S-diglycidyl ether. At least one.

In a preferred embodiment, the bifunctional or higher functional compound (a ₂ ) is a polycarbodiimide.

In a preferred embodiment, the bifunctional or higher functional compound (a ₂ ) is a bisoxazoline compound.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) a thermoplastic polyester elastomer (a ₁₎ a polyester block copolymer polyester type block copolymer used in the flame retardant polyester elastomer composition of the present invention (a ₁₎ is used is known per se that obtain. This polyester type block copolymer is obtained by reacting (i) a crystalline aromatic polyester with (ii) a lactone.

The crystalline aromatic polyester (i) mainly has only an ester bond and has at least one ester bond.
A kind of aromatic group as a main repeating unit, and a crystalline aromatic polyester having a hydroxyl group at a molecular terminal, or an ester bond and an ether bond, and at least one kind of aromatic group as a main repeating unit; and A crystalline aromatic polyester having a hydroxyl group at a molecular terminal may be used.

The crystalline aromatic polyester (i) is
From the viewpoint of improving crystallinity, heat resistance and the like, the polymer skeleton preferably has a C ₁ -C ₁₇ methylene group.

Examples of the crystalline aromatic polyester (i) include homopolymerized polyesters such as polyethylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalate; Polyester ethers such as benzoate and poly-p-phenylenebisoxyethoxy terephthalate; mainly consisting of tetramethylene terephthalate units or ethylene terephthalate units, and additionally tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units, tetramethylene or ethylene seba Kate unit, 1,4-cyclohexylene dimethylene terephthalate unit, tetramethylene or ethylene-p-oxybenzene Such as copolyester or copolyester ether having a copolymerization component such as Zoeto units and the like. These may be used alone or in combination of two or more.

The crystalline aromatic polyester (i) has a melting point of preferably 150 ° C. or higher, more preferably 200 ° C.
° C or higher.

The molecular weight of the crystalline aromatic polyester (i) can vary depending on the application. For example, when used as a molding material, the molecular weight is preferably 5000
The number is more preferably 8000 or more. When used as an adhesive or a coating agent, the molecular weight is preferably 5000 or less, more preferably 3500 or less.

When a copolymer such as a copolymerized polyester or a copolymerized polyester ether is used as the crystalline aromatic polyester (i), a tetramethylene terephthalate unit or a tetramethylene terephthalate unit is used from the viewpoint of improving the crystallinity and heat resistance. It is preferable that the ethylene terephthalate unit is contained in a proportion of 60 mol% or more.

The polyester type block copolymer (a)
_The lactones (ii) used in ₁ ) include caprolactone, enantholactone, caprylolactone and the like. These lactones can be used alone or in combination of two or more. Caprolactone is most preferred from the viewpoint of improving flexibility and heat resistance.

By reacting the crystalline aromatic polyester (i) with the lactone (ii), a polyester type block copolymer (a ₁ ) is obtained. The reaction is
Usually, under a nitrogen atmosphere, at a temperature of 200 ° C to 250 ° C,
The melting reaction is performed for 0.5 to 3 hours, and then the unreacted lactone is removed under vacuum.

The copolymerization ratio of the crystalline aromatic polyester (i) and the lactone (ii) can be appropriately changed depending on the use. In general, when the proportion of the crystalline aromatic polyester (i) increases, the resulting composition becomes harder and the mechanical properties such as strength and elongation are improved. As the proportion of lactones increases, the resulting composition softens and improves low temperature properties. Therefore, the copolymerization ratio of the two can be selected according to the application while considering the balance between the mechanical strength and the low-temperature characteristics.

In general, the copolymerization ratio of the crystalline aromatic polyester (i) and the lactone (ii) is in the range of 97: 3 to 5:95 by weight, and more generally. Is in the range of 95: 5 to 70:30. When it is desired to obtain a hard molded body, the above ratio is preferably 95: 5 to 7
The range is 0:30.

(A ₂ ) Bifunctional or higher compound The thermoplastic polyester elastomer (A) contains a bifunctional compound as a modifier.

The bifunctional compound (a ₂ ) has the following formula (I)

[0037]

(Equation 5)

Here, W1 is the weight of the sample before the heat treatment, and W2 is the weight of the sample after the heat treatment. It is preferably 0.05 or less, and two or more functional groups capable of reacting with the terminal group of the polyester type block copolymer (a ₁ ) in the same molecule, preferably
It has two to four, more preferably two or three.

If the heating loss ratio exceeds 0.1,
The compound (a ₂ ) having a functionality higher than that contains a large amount of volatile components, and as a result, there arises a disadvantage that unreacted substances volatilize during heating.

The polyester type block copolymer (a)
_If the number of functional groups capable of reacting with the terminal group of ₁ ) is less than 2,
The desired mechanical strength cannot be obtained in the obtained thermoplastic polyester elastomer (A).

The structure of the bifunctional or more functional compound (a ₂ ) used in the present invention is not limited as long as it satisfies the above formula (I).

Such a compound having _two or more functionalities (a ₂ )
As, bisphenol A-diglycidyl ether,
Examples include bisphenol F-diglycidyl ether, bisphenol S-syglycidyl ether, cresol novolak glycidyl ether, phenol novolak glycidyl ether, polycarbodiimide, and bisoxazoline compounds. These can be used alone or in combination of two or more.

From the viewpoint of improving volatility and reactivity,
Bisphenol F-diglycidyl ether, polycarbodiimide and bisoxazoline compounds are preferred.

(A ₃ ) Monofunctional Compound The thermoplastic polyester elastomer (A) may further contain, if necessary, a monofunctional compound (a
₃ ) can be used. This monofunctional compound (a ₃ ) is a compound having one functional group capable of reacting with the terminal group of the polyester type block copolymer (a ₁ ). There is no limitation on the structure of the compound as long as it satisfies such conditions.

Examples of such a monofunctional compound (a ₃ ) include polyethylene glycol-monoglycidyl ether, pt-butylphenyl glycidyl ether, allyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, p-phenylphenyl glycidyl ether, Monooxazoline and the like.
These can be used alone or in combination.

From the viewpoint of improving the reactivity, polyethylene glycol-monoglycidyl ether and pt-butylphenylglycidyl ether are preferred.

The thermoplastic polyester elastomer (A) used in the flame-retardant polyester elastomer composition of the present invention comprises, as described later, the above-mentioned polyester type block copolymer (a ₁ ) and the above-mentioned bifunctional or higher functional compound. (A ₂ )
And, if necessary, the above monofunctional compound (a ₃ ) by reacting with various conventionally known methods.

The compounding ratio of the compound having two or more functionalities (a ₂ ) depends on the amount of the functional group present at the terminal of the polyester type block copolymer (a ₁ ) to be used and / or the flame retardancy finally obtained. Although it may vary depending on the properties required for the polyester elastomer composition, 0.1 to 10 parts by weight, preferably 0.3 to 3 parts by weight, _per 100 parts by weight of the polyester-type block copolymer (a1) is used. 8 parts by weight, more preferably in the range of 0.5 parts by weight to 6 parts by weight. If the compounding ratio of the bifunctional or higher-functional compound (a ₂ ) is less than 0.1 part by weight, the effect obtained by reacting such a compound (a ₂ ) can be obtained.
For example, the effects of improving the moldability, heat resistance and hydrolysis resistance due to the increase in viscosity are not significantly exhibited. If the compounding ratio of the bifunctional or higher-functional compound (a ₂ ) exceeds 10 parts by weight, the unreacted compound remains and the molded product is inferior in quality such as a rough surface shape.

The polyester type block copolymer (a)
_{When the} monofunctional compound (a ₃ ) is used together with the compound (a ₂ ) having ₁ or 2 or more functional groups, the mixing ratio of the monofunctional compound (a ₃ ) is determined by the above-mentioned polyester type block copolymer. relative to (a ₁₎ 100 parts by weight, 10 parts by weight or less, preferably, 0.5 part by weight to 8 parts by weight, more preferably 0.1 part by weight to 5 parts by weight. If the proportion of the monofunctional compound (a ₃ ) exceeds 10 parts by weight,
Volatility of unreacted substances may increase.

The thermoplastic polyester elastomer (A) used in the present invention comprises the above-mentioned polyester-type block copolymer (a ₁ ), a compound having _two or more functionalities (a ₂ ) and, if necessary, a monofunctional one. It can be synthesized by reacting with the compound (a ₃ ). Alternatively, (a ₁ )
(A ₂ ) and, if necessary, (a ₃ ) can be synthesized by heating and kneading and molding with a compound having a triazine group described below.

The reaction between the polyester type block copolymer (a ₁ ), the bifunctional or higher functional compound (a ₂ ) and, if necessary, the monofunctional compound (a ₃ ) uses a catalyst. It can happen with or without. It is preferable to use a catalyst from the viewpoint of promoting the reactivity or improving the affinity.

Examples of the above-mentioned catalysts include amines, phosphorus compounds, and metal salts of a monocarboxylic acid and / or dicarboxylic acid having 10 or more carbon atoms, which belong to Group Ia or IIa of the Periodic Table of the Elements. Can be Trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine; and metal salts of stearic acid such as calcium stearate and sodium stearate are preferred. These catalysts can be used alone or in combination of two or more.

The same effect can be obtained by adding the above-mentioned catalysts all at once or separately.

The amount of the catalyst is usually 3 parts by weight or less, preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polyester type block copolymer (a ₁ ).

(B) Compound Having Triazine Group In the flame-retardant polyester elastomer composition of the present invention, a compound (B) having a triazine group is used as a non-halogen flame retardant.

The compounding ratio of the compound (B) having a triazine group is 0.5 to 50 parts by weight, preferably 2 to 35 parts by weight, based on 100 parts by weight of the thermoplastic polyester elastomer (A). Parts by weight, more preferably 5 to 25 parts by weight. If the compounding ratio of the compound (B) having a triazine group is less than 0.5 part by weight, no effect of improving the flame retardancy is recognized, and if it exceeds 50 parts by weight, the mechanical properties and surface appearance of the molded article are poor. Is not preferred.

Examples of the compound (B) having a triazine group include melamine, melamine cyanurate, melamine phosphate, guanidine sulfamate and the like.

Melamine and / or melamine are preferred in terms of preventing bleed-out and improving surface properties such as appearance and flame retardancy.
Alternatively, melamine cyanurate is preferred, and melamine cyanurate is particularly preferred.

Melamine cyanurate is a salt of melamine and cyanuric acid. In order to improve the mechanical strength and surface properties of a molded article obtained by using the composition of the present invention, these are used alone. Instead, it is preferable to use melamine cyanurate obtained by reacting these in advance. Moreover, it is preferable that the melamine cyanurate be as fine a powder as possible.

More specifically, the average particle size of the melamine cyanurate powder is preferably from 2 μm to 100 μm, more preferably from 2 μm to 100 μm, when an image of the powder taken by a scanning electron microscope (SEM) is analyzed by an image analyzer. It is 2 μm to 70 μm. By selecting melamine cyanurate having such a particle size, melamine cyanurate is uniformly and finely dispersed, and an effect of improving the mechanical strength and surface characteristics of the molded article can be obtained.

This melamine cyanurate is obtained by mixing a mixture of cyanuric acid and melamine in a water slurry, mixing the water slurry well to form both salts into fine particles, and then filtering and drying the slurry. It is a powder and differs from a mere mixture.

The flame-retardant elastomer composition of the present invention may further comprise a fibrous reinforcing material and / or an inorganic filler, if necessary, in addition to the thermoplastic polyester elastomer (A) and the compound (B) having a triazine group. May be contained.

As the fibrous reinforcing material, glass fiber,
Inorganic fibers such as silica glass fibers, alumina fibers, gypsum fibers, ceramic fibers, and asbestos fibers; whiskers such as calcium titanate whiskers and zinc oxide whiskers; and carbon fibers.

As the inorganic filler, talc, wollastonite, kaolin, mica, sericite, clay,
Examples include alumina silicate, glass beads, milled glass fiber, calcium carbonate, silica, and milled carbon fiber.

In order to improve the strength, rigidity, heat resistance, dimensional stability, etc. of the resulting flame-retardant polyester elastomer composition, the fibrous reinforcing material and / or the inorganic filler are usually used in the thermoplastic resin. It can be blended within a range not exceeding 100 parts by weight with respect to 100 parts by weight of the polyester elastomer (A).

The flame-retardant polyester elastomer composition of the present invention may further comprise a conventionally known crystallization accelerator, crystal nucleating agent, antioxidant, ultraviolet absorber, hydrolysis resistance improving agent, depending on the application and purpose. Agents, plasticizers, lubricants, flame retardants, flame retardant auxiliaries, antistatic agents, conductivity improvers, slidability imparting agents, polyfunctional crosslinking agents, impact resistance improvers, coloring agents, and the like. Other types of resins, such as ABS resins, thermoplastic polyurethane resins, etc., may be blended as long as the purpose of the present invention is not compromised.

Using the flame-retardant polyester elastomer composition containing the thermoplastic polyester elastomer (A) and the compound (B) having a triazine group,
A molded article having a desired shape can be manufactured. For this, any conventionally known method can be used. For example, the (A) thermoplastic polyester elastomer, or the respective components _{((a 1) ~ (a} 2) or (a ₁₎ ~
(A ₃ )), (B) a compound having a triazine group and, if necessary, the fibrous reinforcing material and / or the inorganic filler are mixed, and the mixture is heated and kneaded with an extruder, a roll mill, a Hanbury mixer, or the like, thereby obtaining A molded article comprising the flame-retardant polyester elastomer composition of the above object can be obtained. This molded product is a compound (B) having a triazine group in a thermoplastic polyester elastomer (A).
Has a composition in which it is uniformly finely dispersed.

For example, when a twin-screw extruder having an inner diameter of 40 mm is used, each component of the above-mentioned (A) thermoplastic polyester elastomer and (B) a compound having a triazine group are mixed, and the resulting mixture is mixed with 180 parts. By extruding at a temperature of from 0C to 260C, a flame-retardant molded article comprising the composition of the present invention can be obtained.

According to the present invention, the polyester-type block copolymer (A) has excellent inherent properties (eg, tensile properties and flexibility), low volatility during heating, excellent flame retardancy and heat resistance. , And having hydrolysis resistance,
The present invention provides a polyester elastomer composition which does not generate a harmful gas and does not have corrosiveness because it does not contain a halogen-based flame retardant. Therefore, the flame-retardant polyester elastomer composition of the present invention is useful as a molding material for fibers, films, or various molded articles.

[0070]

The present invention is specifically illustrated by the following examples, but the present invention is not limited by these examples. The present invention can be modified and implemented within a range that can conform to the purpose described in the present specification, and all of them are included in the technical scope of the present invention.

In this specification, all “parts” are by weight unless otherwise indicated.

The following Table 1 shows the weight loss ratio (%) when the compounds having two or more functionalities used in the following Examples and Comparative Examples were heat-treated at 200 ° C. for 30 minutes.

[0073]

[Table 1]

(Production Example) Preparation of Polyester Type Block Copolymer (a ₁ ) 70 kg of polytetramethylene terephthalate and 30 kg of ε-caprolactone were placed in a reaction vessel, purged with nitrogen gas, and then melted for 2 hours while stirring at 230 ° C. Reacted. Then, unreacted ε-caprolactone is removed under vacuum to obtain a polyester-type block copolymer (a
₁ ) I got a chip. The obtained polyester type block copolymer has a reduced specific viscosity of 1.163 and an acid value of 6
5 equivalents / 10 ⁶ g and a tensile breaking strength of 370 kg /
cm ² and the tensile elongation at break was 710%.

[0075] (Example 1) chip 100 parts by weight of the polyester block copolymer obtained in Preparation Example 1 (a _1), as bifunctional or more compound (a ₂ -1) bisphenol F- diglycidyl ether 4 parts by weight and a compound having a triazine group (B) having an average particle diameter of 2
10 parts by weight of 0 μm melamine cyanurate (MC-1) was placed in a drum tumbler and stirred at room temperature for 30 minutes. The obtained mixture was extruded at 230 ° C. using a coaxial twin-screw extruder having an inner diameter of 40 mm (model number BT-40, manufactured by Plastics Engineering Laboratory), cooled with water, and cut into chips. The obtained chips were dried at 100 ° C. under reduced pressure to obtain chips of the flame-retardant polyester elastomer composition of the present invention.

[0076] (Example 2) bisphenol F- blending ratio of diglycidyl ether (a ₂ -1) and 1 part by weight,
A chip of the flame-retardant polyester elastomer composition of the present invention was obtained in the same manner as in Example 1, except that the blending ratio of melamine cyanurate (MC-1) was changed to 30 parts by weight.

[0077] The mixing ratio (Example 3) bisphenol F- diglycidyl ether (a ₂ -1) and 8 parts by weight,
Melamine cyanurate having an average particle diameter of 20 μm (MC-
Flame-retardant polyester elastomer composition of the present invention in the same manner as in Example 1 except that melamine cyanurate (MC-2) having an average particle diameter of 70 μm was used in a proportion of 10 parts by weight instead of 1). Got a chip.

Example 4 The mixing ratio of bisphenol F-diglycidyl ether (a ₂ -1) was 3 parts by weight,
Further monofunctional compound (a ₃₎ polyethylene glycol monoglycidyl ether (a ₃ -1) 1 part by weight was added as and the average particle diameter of 70μm, instead of melamine cyanurate having an average particle size of 20 [mu] m (MC-1) In the same manner as in Example 1 except that melamine cyanurate (MC-2) was used in a proportion of 30 parts by weight, a chip of the flame-retardant polyester elastomer composition of the present invention was obtained.

[0079] (Example 5) bisphenol F- used in a proportion of 5 parts by weight of polycarbodiimide (a ₂ -2) in place of diglycidyl ether (a ₂ -1), and the average particle size 20μm of melamine cyanurate (MC-1) Instead of using melamine cyanurate (MC-2) having an average particle diameter of 70 μm at a ratio of 20 parts by weight,
In the same manner as in Example 1, chips of the flame-retardant polyester elastomer composition of the present invention were obtained.

[0080] (Comparative Example 1) bisphenol F- except that the 5 parts by weight blending ratio of diglycidyl ether (a ₂ -1), the average particle diameter of 150μm as the compound (B) containing a triazine group Meraminshia Nurate (MC
A chip of a flame-retardant polyester elastomer composition was obtained in the same manner as in Example 1, except that 0.3 part by weight of -3) was used.

[0081] Instead of (Comparative Example 2) bisphenol F- diglycidyl ether (a ₂ -1), polyethylene glycol - 2 parts by weight of diglycidyl ether (a ₂ '-1), and monofunctional compounds (a ₃ ) 2 polyethylene glycol monoglycidyl ether (a ₃ -1) as
Except for using parts by weight, a flame-retardant polyester elastomer composition chip was obtained in the same manner as in Example 1.

[0082] Polyethylene glycol instead of (Comparative Example 3) bisphenol F- diglycidyl ether (a ₂ -1) - using 3 parts by weight of diglycidyl ether (a ₂ '-1), 1 functional compound (a ₃₎ polyethylene glycol mono glycidyl ether (a ₃ -1) using 1 part by weight, as a compound having a triazine group (B), average particle diameter 20μm melamine cyanurate (MC-
Except for using 60 parts by weight of melamine cyanurate (MC-2) having an average particle diameter of 70 μm instead of 1),
In the same manner as in Example 1, chips of the flame-retardant polyester elastomer composition were obtained.

[0083] (Comparative Example 4) bisphenol F- diglycidyl ether in place of (a ₂ -1), using polycarbodiimide (a ₂ -2) at a ratio of 5 parts by weight, and the compound having a triazine group (B) As an average particle diameter of 20
melamine cyanurate (MC-1) having an average particle diameter of 150 μm instead of
3) A flame-retardant polyester elastomer composition chip was obtained in the same manner as in Example 1 except that 30 parts by weight was used.

The flame-retardant polyester elastomer compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for the following items.

[Tensile Elongation at Break and Tensile Elongation at Break] Using an injection molding machine (Yamashiro Seiki model-SAV),
The chips obtained in each of the above Examples and Comparative Examples were heated and melted, and each was 100 mm × 100 by a known method.
After forming into a flat plate having a size of mm × 2 mm, a dumbbell-shaped No. 3 test piece was punched from each flat plate. Using Tensilon UTM-III manufactured by Toyo Seiki Co., each obtained test piece was stretched at a normal temperature at a speed of 500 mm / min, and the load (kg) when the test piece was broken was measured. The value obtained by dividing the load (kg) at the time of breaking by the initial sectional area (cm ² ) was defined as the tensile breaking strength (kg / cm ² ). Further, the ratio of the elongation of the sample until the test piece was broken to the length of the original sample was defined as the tensile elongation at break (%).

[Volatile] The chips obtained in the above Examples and Comparative Examples were each dried to reduce the water content to 0.03% or less. About 20 g of each chip was collected in a glass weighing bottle having a diameter of 6 cm and a height of 3 cm, and the initial weight (S0)
Was weighed. Then, each glass weighing bottle was placed at 150 ° C. for 2 hours.
Placed in a hot air dryer for hours. After cooling, the weight of the sample after heating (S1) was precisely weighed, and the heating loss rate was calculated by the following equation. The lower the loss on heating, the lower the volatility and the better the sample.

[0087]

(Equation 6)

[Flame Retardancy] Using the chips obtained in each of the above Examples and Comparative Examples, a test was conducted at a thickness of 1/32 inch (0.794 mm) in accordance with the evaluation criteria defined in UL-94. Carried out. The flame retardancy level is V-0> V-1
>V-2> HB.

[Heat Resistance] Using the chips obtained in the above Examples and Comparative Examples, a dumbbell test piece was prepared in accordance with JIS K 6301, and the initial tensile elongation E _a (% ).

Further, another dumbbell test piece was allowed to stand in a hot air dryer at 180 ° C. for 500 hours, taken out, and then subjected to the same method as above to determine the tensile elongation E _b (%). As an index, the tensile elongation retention H (%) was calculated from the following equation.

[0091]

(Equation 7)

The larger the value of the retention of tensile elongation, the more excellent the obtained flame-retardant elastomer composition is in the heat resistance.

[Hydrolysis resistance] Using the chips obtained in each of the above Examples and Comparative Examples, the above dumbbell test piece was prepared, the initial tensile elongation E _a (%) was determined, and another dumbbell was obtained. The test piece was immersed in hot water at 80 ° C. for 600 hours, taken out, and then subjected to a tensile elongation E _b using the same method as described above.
(%) Was determined, and as an index of hydrolysis resistance, the tensile elongation retention H (%) was calculated from the above equation (7). The higher the value of the tensile elongation retention, the higher the flame retardant elastomer composition obtained, the better the hydrolysis resistance.

Tables 2 and 3 show the evaluation results of the flame-retardant polyester elastomer composition of the present invention obtained in the above examples and the polyester composition obtained in the comparative examples.

[0095]

[Table 2]

[0096]

[Table 3]

As is clear from Tables 2 and 3, the polyester type block copolymer (a ₁ ) is a bifunctional or more functional compound satisfying the above formula ( ₁ ), and the functional group thereof is Compounding a thermoplastic polyester elastomer (A) having a specific ratio from the compound (a ₂ ) capable of reacting with the terminal group of the polymer (a ₁ ) with a compound (B) having a triazine group at a specific ratio. The first flame-retardant polyester elastomer composition of Examples 1 to 3 and 5 of the present invention obtained by the above, the above-mentioned constituent components (a ₁ ) and (a ₂ ), and a monofunctional compound (a ₃ )
The flame-retardant polyester elastomer composition of the present invention of Example 3 obtained by blending a thermoplastic polyester elastomer (A) formed from the above and a compound (B) having a triazine group in a specific ratio is as follows: Compared to the flame-retardant polyester elastomer composition obtained in Comparative Example 4 containing a halogen-based flame retardant, it has excellent mechanical strength, heat resistance, and hydrolysis resistance, and has a high volatility during heating. Few. Furthermore, since the flame retardant polyester elastomer composition of the present invention does not contain a halogen-based flame retardant, it does not generate harmful gas and has no corrosiveness.

[0098]

By using the flame-retardant polyester elastomer composition of the present invention, it is possible to obtain an elastomer molded article which is excellent in mechanical strength, heat resistance and hydrolysis resistance and has low volatility upon heating. Furthermore, since the flame retardant polyester elastomer composition of the present invention does not contain a halogen-based flame retardant, it does not generate harmful gas and has no corrosiveness.

Claims (7)

[Claims] 1. A flame-retardant polyester elastomer composition comprising (A) 100 parts by weight of a thermoplastic polyester elastomer and (B) 0.5 to 50 parts by weight of a compound having a triazine group, A thermoplastic elastomer (A) comprising: (a ₁ ) 100 parts by weight of a polyester type block copolymer obtained by reacting (i) a crystalline aromatic polyester with (ii) a lactone; and (a ₂ ) a bifunctional A compound having a heat-reducing property represented by the following formula (I) when heat-treated at 200 ° C. for 30 minutes is 0.1 or less, and the functional group of the compound is the polyester type block copolymer ( A flame-retardant polyester elastomer composition formed from 0.1 part by weight to 10 parts by weight of a compound capable of reacting with the terminal group of a ₁ ): Here, W1 and W2 are the weights of the bifunctional compound before and after the heat treatment, respectively. 2. A flame-retardant polyester elastomer composition comprising (A) 100 parts by weight of a thermoplastic polyester elastomer and (B) 0.5 to 50 parts by weight of a compound having a triazine group, A thermoplastic elastomer (A) comprising: (a ₁ ) 100 parts by weight of a polyester type block copolymer obtained by reacting (i) a crystalline aromatic polyester with (ii) a lactone; (a ₂ ) bifunctionality The above compound, wherein the heat loss ratio represented by the following formula (I) when heat-treated at 200 ° C. for 30 minutes is 0.1 or less, and the functional group is the polyester type block copolymer (a compound 0.1 parts by weight to 10 parts by weight capable of reacting with the end groups of _1), and (a ₃₎ 1 monofunctional having a functional group capable of reacting with the terminal groups of the polyester block copolymer (a ₁₎ Conversion Object 10 parts by weight is formed from the following, the flame retardant polyester elastomer composition: [Number 2] Here, W1 and W2 are the weights of the bifunctional compound before and after the heat treatment, respectively. 3. The compound (B) having a triazine group
Is a flame-retardant polyester elastomer composition according to claim 1 or 2, which is melamine and / or melamine cyanurate. 4. The compound (B) having a triazine group
Is powdery melamine cyanurate, and when the image of the powder taken by a scanning electron microscope (SEM) is analyzed by an image analyzer, the average particle size of the powder is 2 μm.
The flame-retardant polyester elastomer composition according to claim 3, which has a thickness of from 100 to 100 µm. 5. The compound (a ₂ ) having _two or more functional groups,
The flame-retardant polyester elastomer composition according to claim 1 or 2, wherein the composition is at least one selected from the group consisting of bisphenol F-diglycidyl ether, bisphenol A-diglycidyl ether, and bisphenol S-diglycidyl ether. 6. The compound (a ₂ ) having _two or more functionalities,
The flame-retardant polyester elastomer composition according to claim 1 or 2, which is a polycarbodiimide. 7. The compound having _two or more functionalities (a ₂ )
3. The flame-retardant polyester elastomer composition according to claim 1, which is a bisoxazoline compound.