JP3484268B2 - Flame-retardant resin composition and electric wire - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition containing no halogen and having excellent tensile elongation and flexibility, and an electric wire using the flame-retardant resin composition as a coating material. is there.

[0002]

2. Description of the Related Art Thermoplastic elastomers are used as coating materials for electric wires and the like by utilizing various properties such as excellent tensile elongation and flexibility. However, in recent years, there has been an increasing demand for electric wire coating materials that have fire resistance, heat resistance, and flame retardancy as a disaster prevention measure against fires, etc., and that do not generate harmful hydrogen halide gas during combustion. Therefore, a thermoplastic elastomer composition having excellent fire resistance and heat resistance, and imparting flame retardancy without using halogen has been investigated, but among them, the polyester block copolymer has excellent fire resistance and heat resistance. Various methods for making a polyester block copolymer flame-retardant without using halogen have been studied. For example,
Although it is reported that the addition of a small amount of red phosphorus has a flame-retardant effect, the use is very limited due to problems such as handling of red phosphorus. Further, JP-A-53-64259 discloses a flame-retardant thermoplastic elastomer composition obtained by adding melamine to a polyester-polyether copolymer, which is a polyester block copolymer. Is not mentioned. In addition to this, JP-A-5-247261 discloses that thermoplastic elastomers include ammonium phosphate and / or phosphonic acid and 2,4,6-triamino-1,3,3.
A method of adding at least one salt of a 5-triazine derivative and cyanuric acid has been disclosed, but this aims mainly at making flame retardance of a polyolefin-based elastomer, and does not describe a polyester block copolymer.

[0003]

A thermoplastic resin composition which is excellent in heat resistance, fire resistance and flame retardancy, does not contain halogen, has excellent tensile elongation and flexibility, and can be used as an electric wire coating material. Things are desired. The present inventors have conducted intensive research to solve the above problems. As a result, they have found that the polyester block copolymer is extremely excellent in heat resistance, fire resistance, tensile elongation and flexibility, and is optimal for electric wire coating materials. However, since the polyester block copolymer is inherently flammable, flame retardancy is often required when it is used as a wire coating material.

As a method for imparting flame retardancy to a polyester block copolymer, a halogen-based organic compound is generally blended, and a flame retardant aid such as antimony trioxide is added for the purpose of improving flame retardancy. Are used together. However, this method not only produces a very large amount of smoke during combustion, but also produces hydrogen halide gas that is harmful to the human body, and thus poses a problem in terms of fire prevention and other disaster prevention measures and cannot be used as a wire coating material. Therefore, there is a strong demand for a polyester block copolymer excellent in flame retardancy without the above problems and dangers, but it is very difficult to make a polyester block copolymer flame-retardant without using halogen. Due to such difficulty, no effective flame retardant method has been discovered so far. However, the present inventors have polyester block copolymer result of the addition of various formulations for flame retarding without using halogen intensive efforts to, phosphorous compounds to the polyester block copolymer 1 or more及beauty DOO The flame-retardant resin composition obtained by blending two or more compounds in total of one or more lysine compound has heat resistance,
Without impairing properties such as fire resistance, tensile elongation and flexibility,
The inventors have found that there is no problem of generation of hydrogen halide during combustion, and have completed the present invention.

The present invention provides a flame-retardant resin composition containing no halogen, which has excellent tensile elongation, flexibility and oil resistance, and an electric wire having a coating of the flame-retardant resin composition. .

[0006]

Means for Solving the Problems The present invention, (A) a polyester block copolymer, and (C) a phosphorus compound one
More及beauty preparative triazine compound 1 or more in total two or more
A flame-retardant resin composition containing the compound of (1), and an electric wire having the flame-retardant resin composition as a coating on the outside of a conductor. The flame-retardant resin composition of the present invention preferably further contains (B) a polyalkylene terephthalate resin.

Next, each component of the resin composition constituting the flame-retardant resin composition of the present invention will be described.

The polyester block copolymer (A) used in the present invention comprises a hard segment and a soft segment.

The hard segment constituting the polyester block copolymer is mainly composed of polybutylene terephthalate. That is, this hard segment is composed mainly of polyester having terephthalic acid and tetramethylene glycol as main constituents of 60 mol% or more per 100 mol% of dicarboxylic acid component. Aromatic dicarboxylic acids containing benzene ring or naphthalene ring other than terephthalic acid, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and 2 to 1 carbon atoms other than tetramethylene glycol
The diol such as aliphatic diol 2 and alicyclic diol such as cyclohexanedimethanol may be copolymerized.

The soft segment, which is the other element constituting the polyester block copolymer, mainly comprises an aromatic dicarboxylic acid and a long-chain diol having 5 to 12 carbon atoms. That is, the soft segment is mainly composed of a polyester containing 60 mol% or more of aromatic dicarboxylic acid and a long-chain diol having 5 to 12 carbon atoms as a main constituent component per 100 mol% of dicarboxylic acid component, It may be a copolymer of an aromatic, aliphatic or alicyclic dicarboxylic acid other than the aromatic dicarboxylic acid used as the main constituent, or a short chain diol.

The aromatic dicarboxylic acid used as the main component of the soft segment is, for example, phthalic acid, isophthalic acid, terephthalic acid or naphthalenedicarboxylic acid.
Particularly, non-linear dicarboxylic acids such as phthalic acid and isophthalic acid are preferable. The diol used as the main component of the soft segment is an aliphatic diol having 5 to 12 carbon atoms, and specific examples thereof include hexamethylene glycol, decamethylene glycol, 3-methylpentanediol and 2-methyloctamethylenediol. is there.

Examples of the aliphatic dicarboxylic acid and alicyclic dicarboxylic acid which can be copolymerized with the soft segment and used include linear dicarboxylic acids having 4 to 12 carbon atoms, and particularly 8 carbon atoms. .About.12 linear dicarboxylic acids and cyclohexanedicarboxylic acids are preferred. Examples of the short-chain diol that can be copolymerized with the soft segment and used include linear aliphatic diols having 2 to 4 carbon atoms, specifically, diethylene glycol.

The (A) polyester block copolymer used in the present invention is the polyester block copolymer comprising the above-mentioned hard segment and soft segment, and the ratio of the hard segment and the soft segment is 1: 4 by weight. It is preferably in the range of 4: 1.
That is, it is preferable that the soft segment is contained in an amount of 80 wt% to 20 wt% with respect to the hard segment of 20 wt% to 80 wt%.

The polyalkylene terephthalate resin (B) used in the present invention is a polymer or copolymer mainly composed of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. Obtained by a condensation reaction. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, and ester-forming derivatives thereof. Examples of the diol component include ethylene glycol,
Examples thereof include aliphatic glycols such as tetramethylene glycol and hexamethylene glycol, diols having an aromatic ring such as 1,4-bisoxyethoxybenzene and bisphenol A, and ester-forming derivatives thereof. Among these, polybutylene terephthalate composed of terephthalic acid or its ester-forming derivative and tetramethylene glycol is preferable.

In the present invention, the polyalkylene terephthalate resin (B) is not always an essential component,
It is preferably contained in the range of 9 times or less the weight of the polyester block copolymer (A).

The resin composition and the electric wire of the present invention are (C)
Phosphorus compound (C-1) 1 or more及beauty preparative triazine (C-
2) One or more kinds in total , containing two or more kinds of compounds.

The (C-1) phosphorus compound used in the present invention has a phosphorus content of 5 to 33% and a carbon number of 0 to 10.
Preferred examples of the phosphorus compound of 0 are triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl resorcinyl phosphate, phenyl diresorcinyl phosphate, dicresol resorcinyl phosphate, diphenyl. Hydroquinyl phosphate,
Dialkyl hydroxymethyl phosphonate, tris (2,
6-dimethylphenyl) phosphate, tris (2,2
4,6-trimethylphenyl) phosphate, tris (2,6-dimethylphenyl) thiophosphate, tris (2,3,6-trimethylphenyl) thiophosphate, bis (2,6-dimethylphenyl) cresylphosphate, bis ( 2,6-dimethylphenyl) naphthyl phosphate, bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), polyphosphoric acid amide, and ammonium polyphosphoric acid.

The (C-2) triazine compound used in the present invention has a carbon number of 3 to 50 and a nitrogen content of 20.
To 80% of 2,4,6-triamino-1,3,5-triazine derivative, cyanuric acid derivative and isocyanuric acid derivative, and specifically, for example, melamine, melamine cyanurate, tris (2-hydroxyethyl) isocyanate Nurate, tris (3-hydroxy-N-propyl) isocyanurate.

(C-1) phosphorus compound and / or (C-
2) As the triazine compound, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. Preferably, a total of 2 or more of (C-1) phosphorus compound and 1 or more of (C-2) triazine compound
Use more than one type of compound.

In the present invention, the total weight of the (C) phosphorus compound and / or the triazine compound is 5 to 150 per 100 parts by weight of the mixture of the (A) polyester block copolymer and the (B) polyalkylene terephthalate resin. It is blended so as to have a content of parts by weight.

Preferably, one or more kinds of (C-1) are added to 100 parts by weight of a mixture of (A) polyester block copolymer and (B) polyalkylene terephthalate resin.
5 to 50 parts by weight of phosphorus compound and one or more kinds of (C-2)
It is blended so as to contain 5 to 50 parts by weight of the triazine compound.

Further, the composition used in the present invention includes
Further, in order to impart desired characteristics depending on the purpose, known additives may be added.

Examples of the additives include antioxidants, antistatic agents, surfactants, heat stabilizers, light stabilizers, nucleating agents, plasticizers, lubricants, release agents, and coloring agents including dyes and pigments. is there.

The resin composition used in the present invention is prepared by
It is prepared by known equipment and methods generally used as a conventional resin composition preparation method. For example, (a) after mixing the components, melt-kneading with an extruder, and then water-cooling with a cooling bath to prepare pellets, (b) pellets with different compositions are prepared, and the pellets are prepared immediately before molding. Method of quantitative mixing, (c) 1 or 2 of each component in the molding machine
A method of directly charging the above can be used.

[0025]

EXAMPLES The effects of the present invention will be further described below with reference to examples, but the present invention is not limited to the following examples.

The components used in Examples and Comparative Examples are as follows. Bisphenol A Bis (Dicresyl Phosphate) ...
[Phosflex 580, manufactured by Akzo Kashima] Triphenyl phosphate ... [TPP, manufactured by Daihachi Chemical Industry] Tris (2,6-dimethylphenyl) phosphate ...
[PX-130, manufactured by Daihachi Chemical Industry] Melamine ... [manufactured by Nissan Chemical Industry] melamine cyanurate ... [MC-490, manufactured by Nissan Chemical Industry] In addition, the measurement methods for property evaluation shown in the examples are as follows. (1) LOI (Limited Oxygen Concentration Index) Flame retardant test method for polymeric materials by the oxygen index method (JIS
100 mm x 6.5 mm according to the method of K7201)
A 3 mm strip test piece was cut out and tested. LOI
Means that the higher the value, the higher the flame retardancy. (2) Mechanical properties Dumbbell test pieces (JIS No. 3) obtained by tensile elongation injection molding
The breaking elongation was measured according to JIS K6301.

Reference Example 1 Dimethyl isophthalate 175
Parts by weight, dimethyl sebacate 23 parts by weight, and hexamethylene glycol 140 parts by weight after transesterification with a dibutyltin diacetate catalyst, polycondensed under reduced pressure, intrinsic viscosity 1.06, due to melting of crystals by DSC method An amorphous polyester showing no endothermic peak was obtained. Separately, a polybutylene terephthalate chip having an intrinsic viscosity of 0.98, which was obtained by polycondensation in the same manner, was dried and added in an amount of 107 parts by weight, and reacted at 240 ° C. for 45 minutes, and then phenylphosphone. The reaction was stopped by adding 0.1 part by weight of acid. The polyester block copolymer was taken out and made into chips to be used as a raw material. The melting point of this chip was 190 ° C. and the intrinsic viscosity was 0.93. This is referred to as a polyester block copolymer (ii).

[Reference Example 2] Dimethyl isophthalate 125
By weight, 54 parts by weight of dimethyl sebacate and 140 parts by weight of hexamethylene glycol were transesterified with a dibutyltin diacetate catalyst and then polycondensed under reduced pressure to obtain a polyester having an intrinsic viscosity of 1.06. This polyester was blocked in the same manner as in Reference Example 1 and then made into chips (polyester block copolymer). This is referred to as a polyester block copolymer (b).

Reference Example 3 Polyester Block Copolymer Containing Polybutylene Terephthalate Same as Reference Example 1 In Reference Example 1, except that the addition amount of polybutylene terephthalate was 150 parts by weight. Similarly, a polyester block copolymer was obtained. This polyester block copolymer had a melting point of 218 ° C. and an intrinsic viscosity of 0.91. This is referred to as a polyester block copolymer (C).

[0030]

[Table 1]

Example 1 A mixture of 90 parts by weight of the polyester block copolymer (a) of Reference Example 1 and 10 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 0.93 was dried at 120 ° C. for 3 hours, and then Table 2
The components described were mixed at the blending ratio (unit: parts by weight) shown in Table 2, melt-extruded with an extruder having a cylinder temperature of 240 ° C., cooled, and made into chips. This chip was injection-molded at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C. under the condition of a molding cycle of 40 seconds, and the tensile elongation and flame retardancy of the obtained molded product were evaluated. The results are shown in Table 2.

[Examples 2 to 3 ] A mixture of 70 parts by weight of the polyester block copolymer (b) of Reference Example 2 and 30 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 0.93 was dried at 120 ° C for 3 hours, Table 2
The components described were mixed at the blending ratio (unit: parts by weight) described in Table 2, and the same examination as in Example 1 was carried out. The results are shown in Table 2.
Shown in.

[Examples 4 to 5 ] A mixture of 30 parts by weight of the polyester block copolymer (C) of Reference Example 3 and 70 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 0.93 was dried at 120 ° C for 3 hours, Table 2
The components described were mixed at the blending ratio (unit: parts by weight) described in Table 2, and the same examination as in Example 1 was carried out. The results are shown in Table 2.
Shown in.

[0034]

[Table 2]

[Comparative Examples 1 and 2] 90 parts by weight of the polyester block copolymer (a) of Reference Example 1 and an intrinsic viscosity of 0.93
The mixture with 10 parts by weight of polybutylene terephthalate was dried at 120 ° C. for 3 hours, and then the components shown in Table 3 were mixed at the blending ratio (unit: parts by weight) shown in Table 3 to obtain the same mixture as in Examples 1 to 3. A study was conducted. The results are shown in Table 3.

Comparative Example 3 12 parts of a mixture of 70 parts by weight of the polyester block copolymer (b) of Reference Example 2 and 30 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 0.93 was used.
After drying at 0 ° C. for 3 hours, the components shown in Table 3 were mixed at the blending ratio shown in Table 3 (unit: parts by weight), and the same examination as in Examples 1 to 3 was carried out. The results are shown in Table 3.

[Comparative Examples 4 to 5] 30 parts by weight of the polyester block copolymer (C) of Reference Example 3 and an intrinsic viscosity of 0.93.
The mixture with 70 parts by weight of polybutylene terephthalate was dried at 120 ° C. for 3 hours, and then the components shown in Table 3 were mixed at the compounding ratio (unit: parts by weight) shown in Table 3 to obtain a mixture in the same manner as in Examples 1 to 3. A study was conducted. The results are shown in Table 3.

[0038]

[Table 3]

As is clear from the above Examples and Comparative Examples, the composition comprising the composition and blending amount of the present invention exhibits excellent flame retardancy and tensile elongation.

[0040]

[Effect of the Invention] (1) a polyester block copolymer and a phosphorus compound 1 or more及beauty preparative triazine compound one
By using the above-mentioned two or more kinds of compounds in total , a high flame-retardant effect was achieved as compared with other conventional flame-retardant techniques for polyester elastomers not using halogen. (2) The resin composition obtained by the present invention is not only good in flame retardancy but also excellent in heat resistance, fire resistance, tensile elongation and flexibility, and is useful as a wire coating material for fire prevention measures such as fire. Is. (3) Since the resin composition of the present invention is made flame-retardant without using halogen, there is no concern about generation of harmful gas such as hydrogen halide during molding, use, or incineration after disposal.

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Claims (2)

(57) [Claims] 1. A dicarboxylic acid component (A) terephthalic acid and tetramethylene glycol each of which is 100 mol%
20 to 80% by weight of a hard segment containing 60% by mole or more of polybutylene terephthalate as a main component, and 60% by mole or more of an aromatic dicarboxylic acid and a long-chain diol having 5 to 12 carbon atoms per 100% by mole of the dicarboxylic acid component. 100% by weight of a polyester block copolymer consisting of 80 to 20% by weight of a soft segment whose main component is polyester, and a mixture 100 of 0 to 90 parts by weight of a (B) polyalkylene terephthalate resin.
The weight part, (C) a phosphorus compound of one or more及beauty preparative rear <br/> Gin Compound 1 or more in total two or more on the compound 5-1
A flame-retardant resin composition containing 50 parts by weight. 2. An electric wire comprising the flame-retardant resin composition according to claim 1 as an electric wire coating material on the outside of a conductor.