JP2638127B2 - Flame retardant polyester type block copolymer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester-type block copolymer composition having excellent flame retardancy.

(Prior art) Polyester-type block copolymers have a wide range of properties from flexible rubber-like elastomers to plastics, and are usually molded by molding thermoplastics, such as injection molding and extrusion molding. Thus, various shaped articles can be formed. Moreover, since they are excellent in heat resistance, various mechanical properties, chemical resistance, weather resistance, and the like, their application range is expanding more and more. On the other hand, polyester-type block copolymers are plastic and cannot be used as such in fields requiring flame retardancy.

Since the polyester type block copolymer has a low melting point soft segment, it is more flammable than ordinary polyester, and it is necessary to add a considerably large amount of a flame retardant to make it flame retardant. The most effective type of the flame retardant is a halogen-based flame retardant, and an antimony compound is generally used as a flame retardant aid.

(Problems to be Solved by the Invention) When a halogen-based flame retardant or an antimony compound is added in a large amount, flexibility, which is a major feature of the polyester type block copolymer, is lost, and the moldability and impact resistance are reduced. On the other hand, the other properties are undesirably reduced, but the self-extinguishing property and the non-drip property are insufficiently imparted, and the flame retardancy cannot be improved to a satisfactory level.

The present inventors have conducted intensive studies to impart excellent flame retardancy without impairing the flexibility, moldability, impact resistance and other properties inherent in the polyester type block copolymer as much as possible.

(Means for Solving the Problems) The present invention relates to (a) halogen-substituted phenyl in 100 parts by weight of a polyester type block copolymer having an aromatic polyester segment and an aliphatic polyether segment and / or a polylactone segment. (B) 1 to 25 parts by weight of organic or inorganic antimony compound (c) Triazine compound and / or derivative thereof
The present invention relates to a polyester-type block copolymer composition having excellent flame retardancy, which is blended with 0.5 to 10 parts by weight.

The polyester type block copolymer used in the present invention is a copolymer having an aromatic polyester segment and an aliphatic polyether segment and / or a polylactone segment, and includes a polyester / polyether copolymer or a polyester / polylactone copolymer.

As the polyester / polyether copolymer used in the present invention, a crystalline aromatic polyester segment comprising an ester unit of a dicarboxylic acid mainly composed of an aromatic dicarboxylic acid having a molecular weight of less than about 300 and a glycol having a molecular weight of less than about 250 And an aliphatic polyether segment comprising a polyalkylene glycol having a molecular weight of about 400 to 6000.

Examples of the dicarboxylic acid constituting the crystalline aromatic polyester segment include aromatic dicarboxylic acids having a molecular weight of less than about 300, such as terephthalic acid, isophthalic acid, phthalic acid, 2,6- and 1,5-naphthalenedicarboxylic acid, and the like. And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as oxalic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dimer acid. These dicarboxylic acids are 2
There may be more than one species.

About 25 constituting the crystalline aromatic polyester segment
Glycols having a molecular weight smaller than 0 include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol,
Alkylene glycols such as 1,6-hexanediol,
And cycloalkylene glycols such as 1,4-cyclohexanedimethanol. These glycols may be two or more kinds.

Preferred examples of the crystalline aromatic polyester segment include polybutylene terephthalate, polybutylene terephthalate / polybutylene phthalate, polybutylene terephthalate / polybutylene isophthalate, polybutylene terephthalate / polybutylene sebacate, polybutylene terephthalate / polyhexamethylene isolate Examples include homopolyesters such as phthalate, polyethylene terephthalate / polyethylene isophthalate, and polyhexamethylene terephthalate, and copolyesters.

About 400-600 that make up the aliphatic polyether segment
Examples of the polyalkylene glycol having a molecular weight of 0 include polyethylene glycol, poly (1,2- or 1,3-
(Propylene oxide) glycol, poly (tetramethylene oxide) glycol, and a copolymer of ethylene oxide and propylene oxide. The molecular weight of the polyalkylene glycol is about 400-6000, preferably about 500
~ 4500. These polyalkylene glycols are 2
There may be more than one species.

Preferred examples of the aliphatic polyether segment include poly (tetramethylene oxide) glycol.

In the polyester / polyether copolymer, the ratio of the crystalline aromatic polyester segment to the aliphatic polyether segment is 90/10 to 10/90 (weight ratio). When the ratio exceeds 90/10, the low-temperature properties cannot be improved because the polyalkylene glycol unit, which is a low Tg component of the polymer, is small, and when the ratio is less than 10/90, the properties of the hard segment of the polymer almost disappear. Would.

Although the method for producing the polyester / polyether copolymer is arbitrary, an example of a suitable polymerization method is to use dimethyl ester of dicarboxylic acid in an excess mole number, that is, about
In the presence of a conventional esterification catalyst together with 1.2 to 2.0 moles of low molecular weight glycol and poly (alkylene oxide) glycol, heat exchange reaction is carried out under normal pressure at a temperature of about 150 to 260 ° C to carry out transesterification to distill methanol, Then, it can be produced by heat polycondensation at about 200 to 270 ° C. under reduced pressure of 5 mmHg or less. If necessary, a component capable of partially chemically cross-linking the polystyrene / polyether copolymer is introduced, and for example, tricarboxylic or more functional polycarboxylic acid, polyol, or polyoxy acid is copolymerized as a part of dicarboxylic acid or glycol to be elastically elastic. It is also possible to improve the properties.

The polyester / polylactone copolymer used in the present invention is a polymer mainly composed of an ester bond or an ester bond and an ether bond, and a crystalline aromatic polyester segment having a main repeating unit containing at least one aromatic group. There are polymers composed of polylactone segments.

Examples of the dicarboxylic acids constituting the crystalline aromatic polyester segment include aromatic dicarboxylic acids having a molecular weight of less than about 300 such as terephthalic acid, isophthalic acid, phthalic acid, 2,6- and 1,5-naphthalenedicarboxylic acid, and the like. Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, oxalic acid, glutaric acid, adipic acid,
Aliphatic dicarboxylic acids such as azelaic acid and sebacic acid; These dicarboxylic acids may be of two or more kinds. Examples of the oxycarboxylic acid constituting the crystalline aromatic polyester segment include p-oxybenzoic acid and the like.

About 25 constituting the crystalline aromatic polyester segment
Glycols having a molecular weight smaller than 0 include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol,
Alkylene glycols such as 1,6-hexanediol,
And cycloalkylene glycols such as 1,4-cyclohexanedimethanol. These glycols may be two or more kinds.

Preferred specific examples of the crystalline aromatic polyester segment include polyethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, homopolyesters such as polyethylene-2,6-naphthalate, polyethylene oxybenzoate, Polyester ethers such as poly-p-phenylenebisoxyethoxy terephthalate, mainly consisting of ethylene terephthalate units or butylene terephthalate units, and other ethylene isophthalate units, butylene isophthalate units, ethylene adipate units,
Copolymer having copolymer components such as butylene adipate unit, ethylene sebacate unit, butylene sebacate unit, 1,4-cyclohexylene dimethylene terephthalate unit and ethylene-p-oxybenzoate unit in an amount of 40 mol% or less of the whole. Examples include polyester or copolymerized polyester ether.

As the lactone constituting the polylactone segment, ε-caprolactone is most preferred, and other enantholactones and caprylolactones are also used. Two or more lactones may be used.

In the polyester / polylactone copolymer, the ratio of the crystalline aromatic polyester segment to the polylactone segment is from 20/80 to 95/5 (weight ratio).

The method for producing the polyester-polylactone copolymer is arbitrary, but an example of a suitable polymerization method is a method in which lactone is reacted with a crystalline aromatic polyester produced according to a conventional method. The reaction may be uncatalyzed, but is significantly accelerated by using a catalyst. When the reaction is carried out in a solventless system, the reaction temperature is a temperature not lower than the temperature at which the mixture of the aromatic polyester and the lactone is uniformly melted, and not lower than the melting point of the produced block polymer.
The reaction in a solvent system can employ an appropriate temperature. Therefore, although it depends on the kind of the aromatic polyester used and the composition ratio with the lactone, a range of about 180 to 260 ° C. is generally preferable.

Examples of the compound having a halogen-substituted phenyl group used in the present invention include compounds represented by the following general formulas (I) to (VIII) and all compounds having a halogen-substituted phenyl group.

(Wherein X represents a chlorine atom or a bromine atom, R ₁ is a hydrogen atom,
An alkyl group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a group which is a halide or hydroxide thereof; R ₃ represents an alkyl group, an aryl group;
Represents an oxygen atom or a sulfur atom.

M and n are integers of 1 to 5, p and q are integers of 1 to 4, r is an integer of 1 to 50, and particularly preferably an integer of 6 to 15.

Although the terminal structures of the general formulas (IV) to (VIII) are arbitrary, halogen-substituted phenols are particularly preferred for (IV) and (V), and (VIII) may be an epoxy group. .

These halogen-based flame retardants are generally used in ordinary thermoplastic resins. However, from the viewpoint of compatibility with the polyester-type block copolymer, general formulas (IV) to (VI)
The compound having a melting point of II) of from 180 to 240 ° C. is preferred. From the viewpoint of the flame retardant effect, those of the general formulas (I) and (III) where m + n = 10 are preferable.

The addition amount of the compound having a halogen-substituted phenyl group shown above is 5 to 50 parts by weight, the flame retardant effect is not recognized below this, and above this, the original physical properties of the polyester type block copolymer are not observed. Extremely low. A particularly preferred addition amount is 8 to 30 parts by weight.

Next, examples of the organic or inorganic antimony compound used in the present invention include antimony trioxide, antimony pentoxide, antimony phosphate, antimony caproate, and triphenylantimony, and antimony trioxide is particularly preferred. The addition amount is 1 to 25 parts by weight, particularly preferably 3 to 15 parts by weight.

Further, as the triazine compound and / or derivative thereof used in the present invention, aminotriazines such as melamine, acetoguanamine, benzoguanamine, phenylacetoguanamine and the like represented by the general formula (IX) and derivatives thereof, general formula (X), (X) Oxytriazines such as cyanuric acid represented by XI) and derivatives thereof, and adducts of aminotriazine and oxytriazine.

(In the formula, R ₁ , R ₂ , and R ₃ are a hydrogen atom, an amino group, an alkyl group, an aryl group, and a phenyl group, and R ₁ , R ₂ , and R ₃ may be the same or different.) (In the formula, R ₁ , R ₂ , and R ₃ are a hydrogen atom, an amino group, an alkyl group, an aryl group, and a phenyl group, and R ₁ , R ₂ , and R ₃ may be the same or different.) (In the formula, R ₁ , R ₂ , and R ₃ are a hydrogen atom, an amino group, an alkyl group, an aryl group, and a phenyl group, and R ₁ , R ₂ , and R ₃ may be the same or different.) Further, as a derivative of the triazine-based compound, an isocyanate group-containing compound represented by the following general formula may also be mentioned.

R ₁ NCO) _n (where n = 1 to 4, the structure of R ₁ is arbitrary.) Among these, the most common ones are used as urethane raw materials such as MDI and TDI. , N
In the use of those having a ratio of 2 to 4, care must be taken to increase the melt viscosity of the composition due to the reaction with the terminal portion of the polyester type block copolymer.

Among these, melamine cyanurate, which is an adduct of melamine and cyanuric acid, is particularly preferred from the viewpoint that the physical properties of the polyester type block copolymer are not reduced and blooming does not occur.

The triazine compounds and their derivatives listed above have been widely known as flame retardants for polyamide-based thermoplastic resins. The effect is very low and the physical properties are deteriorated, so that it is rarely used as a flame retardant.

In the present invention, 0.5 to 10 parts by weight, particularly preferably 1 to 4 parts by weight, of a triazine compound and / or a derivative thereof is added. This addition amount is equivalent to 1/10 to 1/40 of the addition amount of the compound having a halogen-substituted phenyl group and the organic or inorganic antimony compound, and this amount is sufficient to exhibit the synergistic effect of increasing the flame retardancy. A small amount is sufficient. Conversely, if added in excess, the intrinsic physical properties of the polyester type block copolymer will be reduced.

Methods for blending a polyester-type block copolymer with a halogen-substituted compound having a phenyl group, an organic or inorganic antimony compound, a triazine-based compound and / or a derivative thereof include a uniaxial or biaxial kneader or kneading roll. There is a melt kneading method using a Banbury mixer or the like, but a method using a single-screw or twin-screw kneader is the most efficient.

Further, it is preferable that the composition of the present invention is blended with an antioxidant, an ultraviolet absorber and the like which are known for polyester type block copolymers.

Since the composition obtained by the present invention has excellent flame retardancy and can retain the original flexibility, moldability, impact resistance, and other basic physical properties of the polyester type block copolymer, it can be used in electrical products. It can be applied to a wide range of parts, hoses, tubes and cables. The composition of the present invention can be applied to various molded articles by injection molding, extrusion molding, transfer molding, and blow molding.

(Example) Next, the present invention will be described with reference to examples. The polymers and test methods used in the examples are as follows.

(1) Polymer used in Examples Polymer A: polyester block copolymer polyoxytetramethylene glycol (average molecular weight 10
00), a polytetramethylene terephthalate and polytetramethylene oxide block copolymer produced from dimethyl phthalate and 1,4-butanediol by an ordinary polycondensation method, wherein the low melting point polymer segment composed of polytetramethylene oxide is entirely Occupies about 50% by weight.

Crystal melting point of polymer 190 ° C Reduction specific viscosity 1.9 (phenol / tetrachloroethane (6 /
4) Measured at 30 ° C using a mixed solvent) Polymer B: Polyester block copolymer Polytetramethylene obtained by reacting polytetramethylene terephthalate with ε-caprolactone by a known method (Japanese Patent Publication No. 48-4116) Terephthalate, polycaprolactone block copolymer (reduced specific viscosity 1.16)
A known method using a bifunctional epoxy compound (Japanese
No. 48-4115), wherein the copolymerization ratio of ε-caprolactone is about 30% by weight.

Crystal melting point of polymer 205 ° C Reduction specific viscosity 1.4 (phenol / tetrachloroethane (6 /
4) Measured at 30 ° C. using a mixed solvent) (2) Compound having a halogen-substituted phenyl group used in Examples.

Decabromodiphenyl oxide: Marubishi Yuka Kogyo Co., Ltd.
Nonnene DP-10 TBA carbonate oligomer: BC-58 brominated epoxy oligomer manufactured by GLC: SR manufactured by Sakamoto Pharmaceutical Co., Ltd.
-TBA4000 (3) Antimony compounds used in the examples.

Antimony trioxide: Cookstar's White Star (4) Triazine compounds and derivatives thereof used in Examples.

Melamine cyanurate: MX601 manufactured by Mitsubishi Kasei Kogyo Co., Ltd. Melamine: manufactured by Nissan Chemical Industry Co., Ltd. (5) Method for measuring physical properties described in Examples.

Tensile test: JIS K6301 method (JIS No. 3 dumbbell, thickness 2.0m
m) Izod impact strength: ASTM-D256 Combustion test: UL-94V test method Sample thickness 1/16, 1/8 inch The combustion time was the sum of the combustion times after 5 times each of five samples.

Limiting oxygen index (LOI) method: JIS K7201 (A-1) Examples 1 to 3 25 parts by weight of a compound having a halogen-substituted phenyl group and 7 parts by weight of antimony trioxide in polymer A (100 parts by weight) Parts, 2 parts by weight of melamine cyanurate, 40
The mixture was kneaded and pelletized at a resin temperature of 240 ° C. using a φ2 screw extruder. The measurement results of the physical properties are shown in Table 1.

Comparative Examples 1 to 3 For comparison, Polymer A (100 parts by weight) was prepared by adding 25 parts by weight of a compound having a halogen-substituted phenyl group and 7 parts by weight of antimony trioxide to Examples 1 to 3. Table 1 shows the results of pelletization and measurement of physical properties in the same manner.

Examples 4 to 6 Polymer A (100 parts by weight) was added with 25 parts by weight of a compound having a halogen-substituted phenyl group, 7 parts by weight of antimony trioxide, and 2 parts by weight of melamine. The mixture was pelletized at a temperature of 240 ° C. The measurement results of the physical properties are shown in Table 2.

Examples 7 to 9 25 parts by weight of a compound having a halogen-substituted phenyl group in polymer B (100 parts by weight), 7 parts by weight of antimony trioxide, and 2 parts by weight of melamine cyanurate as in Examples 1 to 3 In addition, a resin temperature of 24
The mixture was pelletized at 5 ° C. The measurement results of the physical properties are shown in Table 3.

Comparative Examples 4 to 6 For comparison, polymer B (100 parts by weight) was added with 25 parts by weight of a compound having a halogen-substituted phenyl group and 7 parts by weight of antimony trioxide, and the same as in Examples 7 to 9 Table 3 shows the results obtained by pelletizing in the same manner and measuring physical properties.

By comparing Examples 1 to 9 with Comparative Examples 1 to 6, Polymer A and Polymer B were equivalent to UL94V-2 even at 1/8 inch without melamine cyanurate or melamine, whereas melamine cyanurate was equivalent. It can be seen that adding 2 parts by weight of improves the equivalent to UL94V-0 at 1/16 inch.

In addition, L. with the addition of melamine cyanurate or melamine.
It can be seen that the OI is also improved.

Comparative Examples 7 to 12 For comparison, 35 parts by weight and 45 parts by weight of a compound having a halogen-substituted phenyl group were added to polymer A (100 parts by weight).
Table 4 shows the results obtained by increasing the parts by weight of antimony trioxide to 10 parts by weight and 13 parts by weight, respectively. The pelletizing method is the same as in Comparative Examples 1 to 3.

When the amount of the compound having a halogen-substituted phenyl group and antimony trioxide are increased, the burning time is shortened and 1 /
Equivalent to UL94V-0 at 8 inches, UL at 45 parts by weight of halogenated phenyl group-containing compound even at 1/16 inch
It is equivalent to 94V-0. However, there is almost no effect of improving the LOI, and the tensile strength at break and elongation and the Izod impact strength are considerably reduced. In other words, when a triazine compound and / or its derivative is added, UL
The addition amount of the halogen compound and the antimony compound to achieve 94V-0 (1/16 inch) may be about half that in the case where the triazine compound and / or its derivative is not added, and the tensile elongation at break is correspondingly increased. In addition, a decrease in physical properties such as Izod impact strength is small. LOI is significantly improved by adding a triazine compound and / or a derivative thereof.

Such an effect of the triazine compound and / or its derivative can be explained by considering a synergistic effect with a halogen compound or an antimony compound.

Example 10 25 parts by weight of BC-58, 7 parts by weight of antimony trioxide and 6 parts by weight of melamine cyanurate were added to 100 parts by weight of polymer A.
Table 5 shows the evaluation results in the case of adding parts by weight.

Comparative Example 13 25 parts by weight of BC-58, 7 parts by weight of antimony trioxide and 12 parts by weight of melamine cyanurate were added to polymer A (100 parts by weight).
Table 5 shows the evaluation results in the case of adding parts by weight.

Comparative Example 14 Table 5 shows the evaluation results when 6 parts by weight of melamine cyanurate was added to polymer A (100 parts by weight).

Comparison of Examples 2 and 10 with Comparative Example 13 shows that the addition of 12 parts by weight of melamine cyanurate lowers the Izod impact strength and further prolongs the burning time. When melamine cyanurate is added in an amount of 10 parts by weight or more, the gloss of the molded article is lost and the appearance is significantly deteriorated.

Further, in Comparative Example 14, it can be seen that only melanmin cyanurate does not contribute to flame retardancy at all.

(Effect of the Invention) In the present invention, a small amount of a triazine-based compound and / or a derivative thereof is added to a conventional combination of a halogen-based flame retardant and an antimony compound when contributing to the flame retardancy of the polyester type block copolymer. Thus, it is possible to obtain a composition having excellent self-extinguishing properties and non-drip properties with little deterioration in bending properties, molding workability and impact resistance.

This composition can be applied to fields such as various parts of electric products, hoses, tubes, and cables which require high flame retardancy, in addition to the physical properties inherent in the polyester type block copolymer.

Claims (1)

(57) [Claims] (1) 100 parts by weight of a polyester type block copolymer having an aromatic polyester segment and an aliphatic polyether segment and / or a polylactone segment: (a) 5 to 50 parts by weight of a compound having a halogen-substituted phenyl group Part (b) 1 to 25 parts by weight of an organic or inorganic antimony compound (c) triazine compound and / or derivative thereof
A flame-retardant polyester-type block copolymer composition comprising 0.5 to 10 parts by weight.