JP2003064257A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyamide elastomer flame retardant resin composition and its moldings having high flame retardancy and antistatic properties, and excellent in molding and processing properties such as mold release properties, hydrolysis resistance and chemical resistance such as solvent crack resistance, while maintaining mechanical properties. SOLUTION: The flame retardant resin composition comprises a thermoplastic polyamide elastomer resin composition and a flame retardant, the thermoplastic polyamide elastomer resin composition comprising (a) a thermoplastic polyamide elastomer resin and (b) a crystalline amide compound in which the terminals of a molecule are sealed with hydrocarbon groups having 7-22C and which has 3 or more amide linkages in a molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a high degree of flame retardancy, molding / workability, particularly mold releasability, and water resistance, hydrolysis resistance, chemical resistance, especially solvent crack resistance of the molded product. The present invention relates to a flame-retardant resin composition having excellent properties and the like, and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, various materials having excellent flexibility and flexibility have been used in various fields. Among them, crosslinked rubber and vinyl chloride resin are widely used because of their characteristics. It was a material. However, in recent years, as environmental problems have become more important, the recyclability of materials has been questioned, and it is urgent to provide alternatives for crosslinked rubber and vinyl chloride resin. Under such circumstances, it is recyclable and energy saving in the manufacturing process,
Thermoplastic elastomers are being widely used as alternative materials because they can save labor.

Among them, the thermoplastic polyamide elastomer resin is excellent in lightness, low temperature impact resistance and flexibility and is promising for various molding applications, and various thermoplastic polyamide elastomer resins have been proposed.

The inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 11-269379.
In the publication, a flame-retardant resin composition composed of a polyamide elastomer, a polymerized fatty acid polyamide and a flame retardant was proposed. However, there has been a demand for a flame-retardant resin composition containing a thermoplastic polyamide elastomer having further water resistance and solvent resistance.

[0005]

The problems to be solved by the present invention include molding / processability such as molding releasability, water resistance of molded products, hydrolysis resistance, and solvent resistance without deterioration of mechanical properties. It is an object of the present invention to provide a thermoplastic polyamide elastomer flame-retardant resin composition having excellent chemical resistance such as crack resistance and a molded article thereof.

[0006]

Means for Solving the Problems As a result of intensive investigations to solve the above problems, the present inventors have found that a composition containing a crystalline amide compound (b) in a specific thermoplastic polyamide elastomer resin (a), More preferably, the above problem can be solved by adding a flame retardant to a composition containing one or more additives selected from the group consisting of a carbodiimide compound (c) and a phenoxy resin (d). The present invention has been completed and the present invention has been completed.

That is, in order to solve the above problems, the present invention provides a flame retardant resin composition containing a thermoplastic resin polyamide elastomer resin composition and a flame retardant, wherein the thermoplastic polyamide elastomer resin composition comprises ) Thermoplastic polyamide elastomer resin, and (b) (b-1) (b-1-
1) a monocarboxylic acid having 7 to 23 carbon atoms and / or
(b-1-2) a monoamine having 7 to 22 carbon atoms, and (b-2) (b-
2-1) Aminocarboxylic acid having 6 or more carbon atoms, (b-2-2)
Lactams having 6 or more carbon atoms, (b-2-3) 2 to 2 carbon atoms
12 diamines and (b-2-4) one or more selected from the group consisting of aliphatic dicarboxylic acids having 6 to 22 carbon atoms, alicyclic dicarboxylic acids or aromatic dicarboxylic acids and their ester derivatives Is an amide compound obtained by reacting with an amide-forming monomer or a monomer capable of forming an amide, wherein the amide compound has a molecular terminal sealed with a hydrocarbon group having 7 to 22 carbon atoms, and has 3 carbon atoms in the molecule. It has one or more amide bonds and has an average molecular weight of 6
A flame-retardant resin composition containing a crystalline amide compound in the range of 00 to 1800 is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyamide elastomer resin composition used in the flame-retardant resin composition of the present invention is
(a) a thermoplastic polyamide elastomer resin and (b) a molecular end is sealed with a hydrocarbon group having 7 to 22 carbon atoms, and has 3 or more amide bonds in the molecule, and an average molecular weight of 600 to 1800 And a crystalline amide compound within the range.

Characteristic of the flame-retardant resin composition of the present invention
The crystalline amide compound (b) will be described first.

Crystalline amide compound (b) used in the present invention
Has a molecular end sealed with a hydrocarbon group having 7 to 22 carbon atoms, and has at least 3 or more amide bonds in the molecule, and has a number average molecular weight of 600 to 1800, preferably a number average molecular weight of 800 to The one of 1200 is used. When the number average molecular weight of the crystalline amide compound is less than 600, a sublimation phenomenon occurs during the production of the thermoplastic polyamide elastomer resin composition, and the desired resin composition cannot be obtained, and the appearance of pellets and molded products It is not preferable because the mechanical strength tends to decrease. When the number average molecular weight of the crystalline amide compound is larger than 1800,
It is not preferable because the crystallization rate of the amide compound tends to be slow. In addition, these crystalline amide compounds may be used alone or in combination of two or more kinds.

Crystalline amide compound (b) used in the present invention
Can be easily produced, for example, according to the following method (1) or (2).

(1) (b-1) (b-1-1) C7-C23
1 mol of monocarboxylic acid and / or 1 mol of (b-1-2) monoamine having 7 to 22 carbon atoms, (b-2) (b-2-1) aminocarboxylic acid having 6 or more carbon atoms, and / Or (b-2-2) A method of conducting a condensation reaction with 1 to 3 mol of a lactam having 6 or more carbon atoms.

(2) (b-1) (b-1-1) C7-C23
Monocarboxylic acid and / or (b-1-2) having 7 to 2 carbon atoms
2 mol of monoamine of 2 and (b-2) (b-2-3) 2 carbon atoms
1 to 4 mol of diamines of 1 to 12 and (b-2-4) 1 to 4 mol of aliphatic, alicyclic or aromatic dicarboxylic acid having 6 to 22 carbon atoms and ester derivative thereof Method.

The monocarboxylic acid (b-1-
1) and monoamine (b-1-2) have a hydrocarbon group having 7 to 22 carbon atoms. The hydrocarbon group contained in these compounds is not particularly limited to saturated or unsaturated, but a saturated hydrocarbon group having 7 to 22 carbon atoms is preferable, and an alkyl group having 14 to 22 carbon atoms is particularly preferable. . Examples of such monocarboxylic acid (b-1-1) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. The monocarboxylic acid used in the above reaction may be an acid anhydride or an ester. Examples of the monoamine (b-1-2) include n-octylamine and n
-Dodecylamine, n-hexadecylamine, n-octadecylamine, etc. are mentioned.

Aminocarboxylic acids having 6 or more carbon atoms (b-2
Examples of -1) include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

Examples of the lactam (b-2-2) having 6 or more carbon atoms include ω-caprolactam, enanthlactam, capryllactam, lauryllactam, ω-laurolactam and the like.

Examples of the diamine (b-2-3) having 2 to 12 carbon atoms include ethylenediamine, hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,2. Aliphatic diamines such as 4 (or 2,4,4) -trimethylhexamethylenediamine; bis-
Examples include alicyclic and aromatic diamines such as (4,4′-aminocyclohexyl) methane, metaxylylenediamine and paraxylylenediamine.

Examples of the aliphatic dicarboxylic acid, alicyclic dicarboxylic acid or aromatic dicarboxylic acid having 6 to 22 carbon atoms and the ester derivative (b-2-4) thereof include adipic acid, pimelic acid and suberic acid. , Azelaic acid, sebacic acid, dodecadioic acid, hexadecanedioic acid, eicosandioic acid, eicosadiendioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, xylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Acid, terephthalic acid, isophthalic acid and their ester derivatives,
And so on.

The crystalline amide compound (b) has a molecular terminal sealed with a hydrocarbon group having 7 to 22 carbon atoms, and has 6 to 2 carbon atoms via at least 3 or more amide bonds.
Two saturated aliphatic hydrocarbon chains are linked.

Next, the thermoplastic polyamide elastomer resin (a) which is the other essential component of the thermoplastic polyamide elastomer resin composition will be described.

The thermoplastic polyamide elastomer resin (a) used in the present invention can be used in the flame-retardant resin composition of the present invention without particular limitation as long as it is a thermoplastic polyamide having a remarkable rubber elasticity. Among such thermoplastic polyamide elastomers, the heat obtained by copolymerizing (I) a polyamide oligomer (a-1) having a carboxyl group and / or an amino group at the terminal group with a polyether polyester (a-2) A plastic polyether ester amide block copolymer, or (II) the polyamide oligomer (a-1) above, and a general formula (1)

[0022]

[Chemical 2]

(In the formula, R ₁ is one or two of a substituted or unsubstituted aliphatic or alicyclic diol having 2 to 54 carbon atoms.
It represents a diol residue selected from a mixture of one or more species. R ₂
Is a dicarboxylic acid residue selected from one or a mixture of two or more kinds of aliphatic or aromatic dicarboxylic acids having 6 to 22 carbon atoms and / or dimer acid having 20 to 48 carbon atoms (dimerized fatty acid) Represents a polymerized fatty acid residue selected from high-purity polymerized fatty acids containing 93% or more and one or a mixture of two or more of these derivatives. ), The number average molecular weight of the repeating unit is 800 to 3,000.
A thermoplastic polyesteramide block copolymer obtained by copolymerization with a polyester (a-3) which is 0 is preferable.

The thermoplastic polyamide elastomer resin (a) used in the present invention has
Those having 5% by mass or more of a unit derived from a component composed of at least a dimer acid having 20 to 48 carbon atoms (dimerized fatty acid) and / or a derivative thereof are preferable.

The polyamide oligomer (a-1) constituting the thermoplastic polyether ester amide block copolymer (I) and the thermoplastic polyester amide block copolymer (II) is 1) Aminocarboxylic acid having 6 or more carbon atoms, (a-1-2) Lactam having 6 or more carbon atoms, (a-1-3) Diamine having 2 to 12 carbon atoms, (a-1-
4) Aliphatic dicarboxylic acid having 6 to 12 carbon atoms, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and ester derivatives thereof, and (a-1-5) dimer acid having 20 to 48 carbon atoms and these One or more polyamide-forming monomers or polyamide-forming monomers selected from the group consisting of ester derivatives, and the obtained polyamide oligomer has a carboxyl group and / or
Or obtain a selected one or more polyamide-forming monomers or the polyamide-forming monomers combinations by polyamide reaction to have an amino group,
It is preferable that the polyamide oligomer has a terminal group terminated with at least one kind of a carboxyl group and / or an amino group.

Further, the polyamide oligomer (a-1) constituting the thermoplastic polyether ester amide block copolymer (I) and the thermoplastic polyester amide block copolymer (II) has 6 carbon atoms. The above aminocarboxylic acids (a-1-1), lactams having 6 or more carbon atoms (a-1-2), diamines having 2 to 12 carbon atoms (a-1-3),
Aliphatic dicarboxylic acid having 6 to 12 carbon atoms, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and ester derivatives thereof, and (a-1-5) dimer acid having 20 to 48 carbon atoms and ester derivative thereof ( a-1-4),
Examples thereof include (b-2-1), (b-2-2), (b-2-3) and (b-2-4).

Dimer acid having 20 to 48 carbon atoms (a-1-
5) is a dimerized fatty acid, and a polymerized fatty acid obtained by polymerizing a monobasic unsaturated fatty acid mainly having at least one double bond or triple bond having 10 to 24 carbon atoms is used. To be Examples of such dimer acid and its ester derivative (a-1-5) include soybean oil fatty acid, tall oil fatty acid, natural animal vegetable oil fatty acid such as rapeseed oil fatty acid, oleic acid, linoleic acid, and erucic acid obtained by purifying them. Examples include polymerized fatty acids polymerized from acids and the like and ester derivatives thereof.

[0028] Commercially available polymerized fatty acids usually contain dimer acid (dimerized fatty acid) as a main component and other raw material fatty acids and fatty acids of trimerization or higher. It is preferable that the content of the embodied fatty acid) is 70% or more, the content of the dimer acid is 93% or more, and that the degree of unsaturation is reduced by hydrogenation. Examples of commercially available products of such polymerized fatty acids include “PRIPOL 1009” and “PRIPOL 1010” manufactured by Unichema, and “ENPOL 1010” manufactured by Henkel. These mixtures and ester derivatives can also be used as polymerized fatty acids.

Further, the polyether polyester (a-2) constituting the thermoplastic polyether ester amide block copolymer of the above (I) is (a-2-1) (a-2-1-1) carbon. Aliphatic dicarboxylic acid having 6 to 12 atoms, alicyclic dicarboxylic acid or aromatic dicarboxylic acid, (a-2-1-2) having 20 to 20 carbon atoms
48 dimer acids, and (a-2-1-3) the polybasic acid described in (a-2-1-1) above and the ester of the polybasic acid described in (a-2-1-2) above. One or more polybasic acids selected from the group consisting of derivatives and / or ester derivatives thereof, and (a-2-2)
(a-2-2-1) Polyoxyalkylene glycol, (a-2-2-
2) Aromatic ring-containing polyether diol, (a-2-2-3) above
The polyhydric alcohol described in (a-2-2-1) and / or the above (a-2
-2-2), a mixture of the polyhydric alcohol and the α, ω-dihydroxy hydrocarbon described in 1), or 2 or more polyhydric alcohols selected from the group consisting of, and having a number average molecular weight of 800 to A polyether polyester obtained by an esterification reaction or a transesterification reaction with a polyhydric alcohol in the range of 3000 is preferable.

The polybasic acid constituting the polyether polyester (a-2) is an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, an alicyclic dicarboxylic acid or an aromatic dicarboxylic acid (a-2-1
-1), a dimer acid having 20 to 48 carbon atoms (a-2-1-2),
One or two selected from the group consisting of the ester derivative of the polybasic acid described in (a-2-1-1) and the ester derivative of the polybasic acid described in (a-2-1-2). The above polybasic acid ester derivative (a-2-1-3), as such polybasic acids, those exemplified in the above (b-2-4), (a-1-5) Can be mentioned. Among these, azelaic acid, sebacic acid, dodecadioic acid, polymerized fatty acid, terephthalic acid, and isophthalic acid are the physical properties and chemical resistance of the polymerizable and thermoplastic polyamide elastomer resin composition, and particularly water resistance (hydrolysis resistance). It is preferable from the viewpoint of solvent crack resistance.

Examples of the polyoxyalkylene glycol (a-2-2-1) constituting the polyether polyester (a-2) include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and ethylene oxide. And a block copolymer or a random copolymer of propylene oxide, a block copolymer or a random copolymer of ethylene oxide and tetrahydrofuran, and the like.

The aromatic ring-containing polyether diol (a-2-2-2) constituting the polyether polyester (a-2) is, for example, a copolymer of a dihydric phenol compound and the above polyoxyalkylene glycol, Examples thereof include an adduct of a dihydric phenol and an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, and a mixture of two or more kinds thereof.

Α, ω-dihydroxy carbonization which can be used by mixing with the polyhydric alcohol described in (a-2-2-1) and / or the polyhydric alcohol described in (a-2-2-2). Examples of hydrogen include polyolefin glycols and hydrogenated polybutadiene glycols obtained by polymerizing olefins and butadiene to form hydroxyl groups at the terminals and hydrogenating the double bonds.

The number average molecular weight of the above polyhydric alcohol (a-2-2) is preferably in the range of 800 to 3000,
The range of 0 to 2000 is particularly preferable. Number average molecular weight is 8
When a polyhydric alcohol of less than 00 is used, the resulting flame-retardant resin composition is inferior in solvent crack resistance, and when the number average molecular weight is more than 3000, compatibility with the polyamide oligomer is poor. However, it tends to be difficult to obtain a good block copolymer, which is not preferable.

The polyester (a-3) represented by the above general formula (1) which constitutes the thermoplastic polyesteramide block copolymer (II) is, for example, (a-3-1) at least one carbon atom. A substituted or unsubstituted aliphatic diol and / or alicyclic diol component having 2 to 12 atoms, and a polymerized fatty acid and ester thereof having 20 to 48 carbon atoms as a main component of a dimer acid (dimerized fatty acid) A polyester obtained from a derivative, (a-3-2) an aliphatic dicarboxylic acid having 6 to 22 carbon atoms or an aromatic dicarboxylic acid and / or an ester derivative component thereof, and a dimer acid having 20 to 48 carbon atoms ( A polyester obtained from a dimer diol derived from a polymerized fatty acid whose main component is a dimerized fatty acid) is included.

The polyester (a-3) can be produced by an esterification reaction between a diol compound described below and a dicarboxylic acid and / or its ester derivative described below.

The diol compound used for producing the polyester (a-3) is preferably a substituted or unsubstituted aliphatic or alicyclic diol compound having 2 to 54 carbon atoms,
Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6 -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3-methyl-
1,5-pentanediol, 2-methyl-2,4 pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propane Diol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,
3-hexanediol, 2-butyl-2-ethyl-1,
Aliphatic polyhydric alcohols such as 3-propanediol; Alicyclics such as cyclopentadiene-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol Examples thereof include polyhydric alcohols; dimer diols obtained by reducing dimer acid (dimerized fatty acid). Among these diol compounds, ethylene glycol, 1,4
-Butanediol, neopentyl glycol, dimer diol are particularly preferred. In addition, these diol compounds may be used alone or in combination of two or more.

A commercially available product of dimer diol, which is a derivative of polymerized fatty acid, is "Pypol (P
ripol 2033 "," Spediol (Spe
ziol) C36 / 2 "," Vespol HP-1000 "manufactured by Toagosei Kagaku Co., and the like.

The dicarboxylic acid and ester derivatives used for producing the polyester (a-3) have 6 carbon atoms.
To 22 aliphatic or aromatic dicarboxylic acids and / or their ester derivatives, polymerized fatty acids containing a dimer acid having 20 to 48 carbon atoms (dimerized fatty acid) as a main component, and / or
Or a derivative thereof, specifically, a dicarboxylic acid and an ester derivative (a-1-4) and a dimer acid described as the raw material of the polyamide oligomer (a-1) having a carboxyl group and / or an amino group at a terminal group. And the compounds exemplified in the ester derivative (a-1-5) thereof.

The number average molecular weight of the polyester (a-3) is 8
The range of 00-3000 is preferable, and the number average molecular weight is 100.
The range of 0 to 2000 is particularly preferable. Polyester (a-
When the number average molecular weight of 3) is less than 800, the resulting flame-retardant resin composition tends to have poor solvent crack resistance, which is not preferable, and the polyester (a-3) has a number average molecular weight of 3,000. If it exceeds, the compatibility with the polyamide oligomer (a-1) tends to be poor, and a good block copolymer cannot be obtained, which is not preferable.

Thermoplastic polyamide elastomer resin (a)
Any method can be adopted as a method for producing the above as long as it is a method capable of obtaining a uniform polymer having a high molecular weight. For example, first, a polyamide oligomer (a-1) having a carboxyl group and / or an amino group at the above-mentioned terminal group is synthesized, and then the above-mentioned polyether polyester (a-2) is synthesized.
Or blend the polyester (a-3) described above, under reduced pressure,
Examples include a method of heating under reaction conditions of 200 ° C. to 300 ° C., advancing the esterification reaction using an esterification catalyst to increase the degree of polymerization.

As the esterification catalyst, known catalysts can be used. For example, phosphoric acid type catalysts such as phosphoric acid, metaphosphoric acid and polyphosphoric acid; titanium type catalysts such as tetrabutyl orthotitanate and tetraisopropyl orthotitanate; Tin-based catalysts such as dibutyltin oxide, dibutyltin laurate and monobutylhydroxytin oxide; tetrabutoxyzirconium, zirconium acetate,
Examples thereof include zirconium-based catalysts such as zirconium octylate.

Thermoplastic polyamide elastomer resin (a)
The mixing ratio of the crystalline amide compound (b) is 100 parts by mass of the thermoplastic polyamide elastomer resin (a).
The crystalline amide compound (b) is preferably in the range of 0.1 to 20 parts by mass, particularly preferably in the range of 0.5 to 15 parts by mass, 1
The range of 10 to 10 parts by mass is more preferable. If the compounding ratio of the crystalline amide compound (b) is less than 0.1 parts by mass, a composition with an improved crystallization rate or solidification rate tends not to be obtained, which is not preferable. When the compounding ratio of (b) is more than 20 parts by mass, the mechanical properties of the thermoplastic polyamide elastomer resin tend to deteriorate, which is not preferable.

The flame-retardant resin composition of the present invention shows excellent water resistance as it is, but if it is assumed that it is used under more severe conditions, the carbodiimide compound (c) is used in combination, or the carbodiimide compound is used. It is more preferable to use (c) and the phenoxy resin (d) together.

The carbodiimide compound (c) used together for such a purpose is a compound having a carbodiimide group in the molecule. Examples of such a carbodiimide compound (c) include diisopropylcarbodiimide, dicyclohexylcarbodiimide, di-o-toluoylcarbodiimide, diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, poly (hexamethylenecarbodiimide), poly (cyclohexylcarbodiimide). Silencarbodiimide), poly (paraphenylenecarbodiimide), poly (metaphenylenecarbodiimide), poly (tricarbodiimide), poly (4,4'-biphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'- Biphenylmethanecarbodiimide), high molecular weight bis (2,6-diisopropylphenyl) carbodiimide and high molecular weight bis (2,4,6-triisopropylphenyl) carbodiimide. To be Among these, di-o-toluoylcarbodiimide, di-2,6
-Dimethylphenylcarbodiimide, poly (triylcarbodiimide), poly (4,4'-biphenylmethanecarbodiimide), high molecular weight bis (2,6-diisopropylphenyl) carbodiimide, bis (2,4,6-
High molecular weight triisopropylphenyl) carbodiimides are particularly preferred.

Similarly, the phenoxy resin (d) used together with the carbodiimide compound (c) is a polycondensation product of epichlorohydrin and bisphenol A, bisphenol F and / or a nuclear substitution product thereof, and has a general formula:

[0047]

[Chemical 3]

(Wherein each of X _{1 to} X ₆ independently represents a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group, or a halogen atom such as chlorine or bromine). It will be. Among these, those which are polycondensates of epichlorohydrin and bisphenol A or bisphenol F and have a number average molecular weight of 10,000 to 75,000 are preferable.

When the carbodiimide compound (c) and the phenoxy resin (d) are used, the compounding ratio of the carbodiimide compound (c) to the thermoplastic polyamide elastomer resin (a) is 100 parts by mass of the thermoplastic polyamide elastomer resin (a). ) 0-10 parts by mass and phenoxy resin (d)
The range of 0 to 20 parts by mass is preferable.

The compounding ratio of the carbodiimide compound (c) is 1
If it exceeds 0 parts by mass, the melt viscosity of the obtained flame-retardant resin composition tends to increase and the moldability tends to deteriorate, such being undesirable. Considering the compatibility with the thermoplastic polyamide elastomer resin (a), the blending ratio of the carbodiimide compound (c) is 1
A range of 0 to 5 parts by mass is particularly preferable with respect to 00 parts by mass.

When the compounding ratio of the phenoxy resin (d) exceeds 20 parts by mass, not only the melt viscosity of the flame-retardant resin composition obtained increases but the moldability deteriorates, but also the flexibility and flexibility of the resin composition Impact resistance tends to decrease, which is not preferable. Considering the compatibility with the thermoplastic polyamide elastomer resin (a), the blending ratio of the phenoxy resin (d) is
0 to 10 parts by mass is preferable, and 0 to 5 parts by mass is particularly preferable, relative to 100 parts by mass of the thermoplastic polyamide elastomer resin (a).

The method for preparing the thermoplastic polyamide elastomer resin composition used in the present invention includes a crystalline amide compound (b) and, if necessary, a carbodiimide compound.
A preferred method is to add (c) and, if necessary, a phenoxy resin (d) during the production of the thermoplastic polyamide elastomer resin (a). Crystalline amide compound (b),
The timing of addition of the carbodiimide compound (c) and the phenoxy resin (d) depends on the thermoplastic polyamide elastomer resin.
From the step of amidating the polyamide-forming monomer in the production step (a) to obtain a polyamide oligomer having a terminal group terminated with at least one of a carboxyl group and / or an amino group, and proceeding to an esterification reaction under reduced pressure. Is more preferable, and any step up to the step of adding an esterification catalyst, advancing the esterification reaction under reduced pressure, and increasing the degree of polymerization is particularly preferable.

The flame retardant used in the present invention is not particularly limited, and various flame retardants can be used. Examples of the flame retardant include a flame retardant composed of a compound having a halogen atom, a flame retardant composed of a metal hydroxide, a flame retardant composed of a compound having a nitrogen atom, a flame retardant composed of a compound having a phosphorus atom, and the like. . Generally, the flame retardant may be selected according to the application and the flame retardant standard, and these flame retardants may be used alone or in combination of two or more kinds.

Examples of the flame retardant composed of a compound having a halogen atom include decabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenylethane, ethylenebistetrabromophthalimide, 1,2,3,4,7. , 8, 9, 10, 13, 1
3,14,14-dodecachloro-1,4,4a, 5
6,6a, 7,10,10a, 11,12,12a-dodecahydro-1,4: 7,10-dimethanodibenzo (a, e) cyclooctene, brominated polystyrene and crosslinked products thereof, ethylene- (5,6- Dibromonorbornane-2,3-dicarboximide), 2,4,6- (tris-2,4,6-tribromophenoxy) -1,3
Examples include 5-triazine, N, N′-bis (tetrabromophthalimide), brominated epoxy, tetrabromobisphenol-A, and derivatives thereof. The flame retardant composed of a compound having a halogen atom is preferably used in combination with a flame retardant aid such as antimony trioxide, antimony pentoxide or zinc borate.

Examples of the flame retardant composed of a metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like. Among these, magnesium hydroxide, which has excellent heat resistance, is particularly preferable. The metal hydroxide is surface-treated with various surface treating agents in order to improve the processability and water resistance of the flame-retardant resin composition containing the metal hydroxide. In the flame-retardant resin composition of the present invention, a surface-treated metal hydroxide can be used. The characteristics of the flame-retardant resin composition containing the surface-treated metal hydroxide are not affected by the type of surface treatment agent and the amount thereof used.

Examples of the flame retardant composed of a compound having a nitrogen atom include melamine cyanurate, melam, melem, melamine, urea and biurea. Among these, melamine cyanurate is particularly preferable in terms of heat resistance and flame retardancy.

Examples of the flame retardant composed of a compound having a phosphorus atom include orthophosphoric acid ester, condensed phosphoric acid ester, phosphoric acid ester amide, guanylurea phosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, polyphosphoric acid. Examples thereof include acid melem and ammonium polyphosphate. Among these, heat resistance, flame retardancy, excellent water resistance, and from the viewpoint of having a plasticizing effect on the polyamide elastomer, orthophosphoric acid ester, condensed phosphoric acid ester,
Phosphoric acid ester amides are particularly preferred.

The preferable range of the blending ratio of the thermoplastic polyamide elastomer resin composition and the flame retardant depends on the kind of the flame retardant used.

When a flame retardant composed of a compound having a halogen atom is used as the flame retardant and is used in combination with a flame retardant auxiliary,
Also, when a flame retardant composed of a compound having a halogen atom and other flame retardants are used in combination, the mixing ratio of the thermoplastic polyamide elastomer resin composition and the flame retardant is 98 to 20% by mass of the thermoplastic polyamide elastomer resin composition,
The flame retardant is preferably in the range of 2 to 80% by mass, and from the viewpoint of maintaining the mechanical properties of the flame retardant resin composition, the mixing ratio of the thermoplastic polyamide elastomer resin composition and the flame retardant is the thermoplastic polyamide elastomer resin composition. A range of 98 to 30 mass% and a flame retardant of 2 to 70 mass% are particularly preferable.

Further, as the flame retardant, a flame retardant composed of a metal hydroxide, a flame retardant composed of a compound having a nitrogen atom, a flame retardant composed of a compound having a phosphorus atom is used alone, or a flame retardant composed of these groups. When used in combination, the mixing ratio of the thermoplastic polyamide elastomer resin composition and the flame retardant is from the viewpoint of maintaining the mechanical properties of the flame retardant resin composition and flame retardancy, the thermoplastic polyamide elastomer resin composition. 90-30% by mass, flame retardant 10-70
A mass% range is preferred.

In addition, when a regular phosphoric acid ester, a condensed phosphoric acid ester or a phosphoric acid ester amide is used among the flame retardants composed of a compound having a phosphorus atom in the flame retardant resin composition, the flame retardant resin composition From the viewpoint of maintaining good processability, the blending ratio of the flame retardant in the flame retardant resin composition is 20.
A mass% or less is particularly preferable.

The flame-retardant resin composition of the present invention has a resistance of 10 ¹³ Ω.
Since it has the following surface resistance, it also has an effect of preventing adhesion of dust. Therefore, it is not necessary to add an antistatic agent such as a surfactant to the flame-retardant resin composition of the present invention.

Other additives may be added to the flame-retardant resin composition of the present invention, if necessary. Other additives include various inorganic compounds; phenolic compounds,
Antioxidants such as thioethers, phosphites, lactones, vitamins; UV absorbers such as benzotriazoles, benzophenones, benzoates, triazines; light stabilizers such as hindered amines; metal deactivators; Silicone-based, fluorine-based, amide-based release agents, anti-meyer agents and lubricants; metal soaps, amide-based dispersants; dyes, organic and inorganic pigments, colorants; crystal nucleating agents; antistatic agents. To be

The flame-retardant resin composition of the present invention is processed into various films, sheets, various molded products, electric wire coating materials, etc. which are excellent in flame retardancy, water resistance, chemical resistance, processability and antistatic property. can do.

The flame-retardant resin composition of the present invention comprises polyethylene, an ethylene-vinyl acetate copolymer and a saponified product thereof, an ethylene-vinyl alcohol copolymer, an ethylene-ethyl acrylate copolymer and a saponified product thereof.
It has excellent compatibility with various resins such as ethylene-methyl methacrylate copolymer, polypropylene, polystyrene, ABS, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, various polyamides, polyester elastomers. Therefore, flame retardancy can be imparted by adding the flame retardant resin composition of the present invention to these resins.

[0066]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the scope of these examples without departing from the spirit of the present invention. In addition, all "%" in the following Examples and Comparative Examples are based on mass.

<Synthesis of Crystalline Amide Compound> (Synthesis Example 1) (Synthesis of Crystalline Amide Compound (PAC-1)) Volume 100 equipped with a stirrer, nitrogen inlet and distillation tube
In a 0 ml 4-neck flask, 340.8 g of stearic acid,
Hexamethylenediamine 139.2 g, sebacic acid 12
1.2 g and xylene 60 g were charged, the temperature was raised to 170 ° C. while flowing a fixed amount of nitrogen, and then the condensation reaction was carried out while distilling off the reaction water at the same temperature. When the inside of the system became a transparent homogeneous solution, the temperature was raised to 250 ° C while distilling xylene and water of reaction, and the dehydration condensation reaction was further advanced. Finally, an acid value and an amine value were prepared so as to be in an equivalent relationship, and reacted under reduced pressure (40 mmHg) to give a crystalline amide compound having a terminal blocked with a stearyl group (17 carbon atoms) ( PAC-1) was obtained. The crystalline amide compound (PAC-1) thus obtained is a white solid having an acid value, an amine value of 0.5 or less and a number average molecular weight of 900, and a melting point of 142 ° C. and a crystallization temperature of 174 ° C. It was

Next, the thermoplastic polyamide elastomer resin composition used in the present invention will be specifically described.
As for the mixing ratio of each raw material illustrated below, the total of the concentration of the carboxyl group and the concentrations of the amino group and the hydroxyl group is in an equivalent relation in principle.

First, a thermoplastic polyamide elastomer resin composition comprising a polyether ester amide block copolymer will be exemplified.

(Synthesis Example 2) (Synthesis of Polyamide Elastomer (PAE-1)) A capacity of 100 equipped with a stirrer, a nitrogen inlet and a distillation tube.
In a 0 ml 4-necked flask, hydrogenated polymerized fatty acid (“Pripol 100” manufactured by Unichema)
9 ") 236.8 g, azelaic acid 134.0 g and hexamethylenediamine 126.1 g are charged, the temperature is raised to 250 ° C. while flowing a certain amount of nitrogen, and dehydration polycondensation reaction is performed at 250 ° C. to obtain an acid value of 5. A transparent polyamide oligomer having 7 mgKOH / g and a number average molecular weight of 8200 was obtained.

Next, at this temperature, the reaction mixture containing the polyamide oligomer was further mixed with 4.4 azelaic acid.
g, polyoxytetramethylene glycol having a hydroxyl equivalent of 512.3, 43.4 g, and "Irganox 1098".
(Antioxidant manufactured by Ciba-Geigy Co., Ltd.)
After uniformly mixing, 1.0 g of tetrabutoxyzirconium as an esterification catalyst was added, the pressure was reduced to 798 Pa, and the reaction was continued for another 30 minutes, whereby the polyamide-forming component was a polycondensate composed of hexamethylenediamine and polymerized fatty acid. To obtain a polyether ester amide block copolymer composed of a copolymer of hexamethylene diamine and azelaic acid.

Next, at the same temperature, the crystalline amide compound (PAC-1) produced in Synthesis Example 1 was added to 10 parts by mass of 100 parts by mass of the polyether ester amide block copolymer.
Add parts by mass, and under reduced pressure until the viscosity becomes constant (133
By continuing the reaction at Pa), a melt viscosity of 144P
a ・ s / 250 ℃, melting point 180 ℃, crystallization temperature 158 ℃
Thermoplastic polyamide elastomer resin composition (PAE
-1) was obtained.

The thermoplastic polyamide elastomer resin composition (PAE-1) after the completion of the reaction was immediately extruded from the extruder into water set at 15 ° C. and strand-cut into pellets.

(Synthesis Example 3) (Synthesis of Polyamide Elastomer (PAE-2)) In Synthesis Example 2, the crystalline amide compound (PAC-1) was used.
Simultaneously with the addition of 0.5 parts by mass of (bis (2,6-diisopropylphenyl) carbodiimide) (100% by mass of polyetheresteramide block copolymer) "Sudabacol P") and 2 parts by mass of phenoxy resin ("PKHH" manufactured by Union Carbide Co., USA) were added in the same manner as in Synthesis Example 2 except that a thermoplastic polyamide elastomer resin composition ( PAE-2) was obtained.

(Synthesis Example 4) (Synthesis of Polyamide Elastomer (PAE-3)) In Synthesis Example 2, the crystalline amide compound (PAC-1) was used.
A thermoplastic polyamide elastomer resin composition (PAE-3) was prepared in the same manner as in Synthesis Example 2 except that the compound was not added.
Got

Next, an example of producing a thermoplastic polyamide elastomer resin composition comprising a polyesteramide block copolymer will be illustrated.

(Synthesis Example 5) (Synthesis of Polyamide Elastomer (PAE-4)) Hydrogenated polymerized fatty acid ("Pripol 100" manufactured by Unichema Co., Ltd. was placed in the same apparatus as in Synthesis Example 2).
9 ") 105.2 g, dodecadioic acid 59.4 g, and hexamethylenediamine 51.4 g were charged, the temperature was raised to 250 ° C while flowing a certain amount of nitrogen, and dehydration polycondensation was performed at 250 ° C to obtain a polyamide oligomer. It was

Next, at this temperature, the reaction mixture containing the polyamide oligomer was further added with 105.
6 g, 105.6 g of "PRIPOL 1009", 112.1 g of 1,10-decanediol having a hydroxyl equivalent of 87 and 1.0 g of "Irganox 1098" (an antioxidant manufactured by Ciba Geigy) were added and mixed uniformly. Then, as an esterification catalyst, tetrabutoxy zirconium 1.0
After the addition of g, the pressure was reduced to 798 Pa, and the reaction was continued for another 30 minutes to obtain a polycondensate containing a hexamethylenediamine and a polymerized fatty acid as a polyamide-forming component, and a polycondensate containing hexamethylenediamine and dodecadioic acid. A polyesteramide block copolymer composed of the copolymer of

Next, at the same temperature, 5 parts by mass of the crystalline amide compound (PAC-1) produced in Synthesis Example 1 was added to 100 parts by mass of the polyesteramide block copolymer, and the viscosity became constant. By continuing the reaction under reduced pressure (133 Pa), a thermoplastic polyamide elastomer resin composition (PAE-4) was obtained.

After the reaction, the thermoplastic polyamide elastomer resin composition (PAE-4) was immediately extruded from the extruder into water set at 15 ° C. and strand-cut into pellets.

(Synthesis Example 6) (Synthesis of Polyamide Elastomer (PAE-5)) In Synthesis Example 5, the crystalline amide compound (PAC-1) was used.
Simultaneously with the addition of the above, a high molecular weight product of (bis (2,6-diisopropylphenyl) carbodiimide corresponding to 0.5 parts by mass relative to 100 parts by mass of the polyesteramide block copolymer (“Chemie manufactured by Rein Chemie” Sudabacol P ”) and a phenoxy resin (“ PKHH ”manufactured by Union Carbide Co., USA) in an amount corresponding to 0.5 parts by mass, in the same manner as in Synthesis Example 5 except that a thermoplastic polyamide elastomer resin composition ( PAE-5) was obtained.

(Synthesis Example 7) (Synthesis of Polyamide Elastomer (PAE-6)) In Synthesis Example 5, the crystalline amide compound (PAC-1) was used.
A thermoplastic polyamide elastomer resin composition (PAE-6) was prepared in the same manner as in Synthesis Example 5, except that the compound was not added.
Got

<Example 1> 7 parts of the thermoplastic polyamide elastomer resin composition (PAE-1) obtained in Synthesis Example 2 was used.
0%, decabromodiphenyl ethane (“SAYTEX 8010” manufactured by Ethyl Corporation) 20%, antimony trioxide (“PATOX-” manufactured by Nippon Seiko Co., Ltd.)
M ") is tumbler blended at a ratio of 10%, and 30 m
After melt-kneading at 200 ° C. using a mφ twin-screw extruder,
Pelletized.

The pellets thus obtained were molded at 200 ° C. by an injection molding method to prepare a 1 mm thick sheet. The prepared 1 mm sheets were stacked and a 3 mm thick sheet was prepared by a hot press and a cooling press. Further, the pellets thus obtained were coated with 0.48 mmφ copper wire by 0.18 mm using an electric wire extruder to prepare an electric wire.

<Example 2> Synthesis example 2 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-1) obtained in step 4 and 55% of magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

Example 3 Synthesis Example 3 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-2) obtained in 5 and magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used at a rate of 55%. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

<Example 4> Synthesis example 3 in Example 1
Except that 70% of the thermoplastic polyamide elastomer resin composition (PAE-2) obtained in step 1 and 30% of melamine cyanurate (“MC-610” manufactured by Nissan Chemical Industries, Ltd.) were used. Pelletization was performed in the same manner as in Example 1 to prepare a sheet and an electric wire.

<Example 5> Synthesis example 3 in Example 1
40% of the thermoplastic polyamide elastomer resin composition (PAE-2) obtained in 1., 55% of magnesium hydroxide ("Kisuma 5A" manufactured by Kyowa Chemical Industry Co., Ltd.), condensed phosphate ester (Asahi Denka Kogyo ( Co., Ltd. "Adeka Stab FP
-600 ") was used in the same manner as in Example 1 except that 5% was used to form a sheet and an electric wire.

Example 6 Synthesis Example 3 in Example 1
40% of the thermoplastic polyamide elastomer resin composition (PAE-2) obtained in 1., 55% of magnesium hydroxide ("Kisuma 5A" manufactured by Kyowa Chemical Industry Co., Ltd.), orthophosphoric acid ester (Dahachi Chemical Industry) 5% of "TPP" manufactured by Co., Ltd.
A sheet and an electric wire were prepared in the same manner as in Example 1 except that the sheet and the electric wire were used.

Example 7 Synthesis Example 3 in Example 1
40% of the thermoplastic polyamide elastomer resin composition (PAE-2) obtained in the above, 55% of magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.), phosphoric ester amide (Shikoku Chemicals ( Co., Ltd. "SP-70
3 ”) was used in the same manner as in Example 1 except that 5%) was used to form a sheet and an electric wire.

Comparative Example 1 Synthesis Example 4 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-3) obtained in 1. and 55% of magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

<Example 8> Synthesis example 5 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-4) obtained in Example 5 and 55% of magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

<Example 9> Synthesis example 6 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-5) obtained in 5 and magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used at a rate of 55%. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

Comparative Example 2 Synthesis Example 7 in Example 1
Example except that 45% of the thermoplastic polyamide elastomer resin composition (PAE-6) obtained in step 4 and 55% of magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd.) were used. In the same manner as in 1, pelletization was performed to prepare a sheet and an electric wire.

<Evaluation> Each sheet and each electric wire obtained in each Example and each Comparative Example was evaluated according to the method described below, and the results are summarized in Tables 1 to 3.

(1) Workability The processability during compound extrusion was judged according to the following criteria. ◯: Good. Δ: Processing is difficult. X: Unprocessable.

(2) Flammability 1 A vertical burning test of UL94 was carried out with a thickness of 3 mm. V-
It was judged whether or not it was compatible with 0 or V-2.

(3) Flammability 2 It was carried out according to the horizontal and tilt tests of JIS C 3005. However, the inclination angles were 30, 45 and 60 degrees.

(4) Tensile elongation It was carried out according to JIS K 7113. At that time, 1
The measurement was performed at a pulling speed of 200 mm / min using a mm thick sheet. The tensile elongation is shown in%.

(5) Alcohol resistance As an example of solvent resistance, alcohol resistance was evaluated. 1 mm
The test piece of the thick sheet was bent, and methanol impregnated in a cotton swab was applied to the maximum bent portion of the bent portion, and the presence or absence of cracks was judged according to the following criteria. ◯: There is no crack. Δ: There are fine cracks. X: There is a crack.

(6) Water resistance A 1 mm thick sheet was kept for 30 days under the conditions of 85 ° C. and 80% humidity, and the residual rate of tensile elongation was judged according to the following criteria. ◯: Remaining rate of 80% or more. Δ: Residual rate 79 to 51%. X: 50% or less of residual rate

(7) Surface resistance According to JIS K 6911, it was measured using a 1 mm thick sheet. It was judged according to the following criteria. ◯: Surface resistance is 10 ¹³ Ω or less. ×: Surface resistance is 10 ¹³ Ω or more

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

<Explanation of Abbreviations in Tables 1 to 3> PAE-1: Polyamide elastomer synthesized in Synthesis Example 2 PAE-2: Polyamide elastomer synthesized in Synthesis Example 3 PAE-3: Polyamide elastomer synthesized in Synthesis Example 4 PAE-4: Polyamide elastomer synthesized in Synthesis Example 5 PAE-5: Polyamide elastomer synthesized in Synthesis Example 6 PAE-6: Polyamide elastomer synthesized in Synthesis Example 7 8010: Decabromodiphenylethane (“SAYTEX 8010 manufactured by Ethyl Corporation ") Sb: Antimony trioxide (" PAT "manufactured by Nippon Seiko Co., Ltd.)
OX-M ") Mg: magnesium hydroxide (" Kisuma 5A "manufactured by Kyowa Chemical Industry Co., Ltd.) MC: melamine cyanurate (" MC-610 "manufactured by Nissan Chemical Industry Co., Ltd.) FP: condensed phosphate ester ("Adeka Stab FP-600" manufactured by Asahi Denka Co., Ltd.) TPP: Orthophosphoric acid ester ("TPP" manufactured by Daihachi Chemical Co., Ltd.) SP: Phosphoric acid ester amide (manufactured by Shikoku Chemicals Co., Ltd.) "SP-703") MEOH resistance: Methanol resistance

From the results shown in Tables 1 to 3, Examples 1 to 4 were obtained.
It can be understood that the flame-retardant resin composition of (1) has high flame retardancy by adding various flame retardants and is excellent in solvent resistance and water resistance. Further, it can be understood that the flame-retardant resin composition using the polyesteramide elastomer resin of Examples 8 to 9 has the same result as the flame-retardant resin composition using the polyetheresteramide elastomer resin. Moreover, the flame-retardant resin compositions of Examples 5 to 7
By adding a flame retardant composed of a compound having a phosphorus atom,
It can be seen that it further improves flame retardancy, mechanical properties and solvent resistance and water resistance. Furthermore, from the comparison between Example 2 and Example 3 or Example 8 and Example 9, the flame-retardant resin composition containing the carbodiimide compound (c), or the carbodiimide compound (c) and the phenoxy resin were added. It can be understood that the flame-retardant resin composition added with (d) has further improved solvent resistance and water resistance. on the other hand,
It can be understood that the flame-retardant resin compositions of Comparative Example 1 and Comparative Example 2 are inferior in solvent resistance and water resistance and cannot be practically used.

[0108]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention has a high level of flame-retardant property without deteriorating mechanical properties, and has antistatic property, and further, has excellent moldability and processability. In particular, it is excellent in mold releasability, water resistance (hydrolysis resistance), chemical resistance, especially solvent crack resistance of the molded product. INDUSTRIAL APPLICABILITY The flame-retardant resin composition of the present invention is easy to process into sheets, films, electric wire coatings, casings, industrial films such as building materials and construction sheets, sheets, adhesive tapes and wallpapers for general household use. It is also useful for applications such as wire coating materials, electronic component molding materials, and combinations with other materials.
It has high industrial value.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C08K 5/29 C08K 5/29 5/3492 5/3492 5/521 5/521 C08L 71/10 C08L 71 / 10 C09K 21/02 C09K 21/02 21/04 21/04 21/10 21/10 21/12 21/12 // (C08L 77/12 C08L 77:00 77:00) F-term (reference) 4F071 AA51 AA54 AA57 AB18 AC12 AC15 AC19 AE07 AF01 AF02 AF38 AF38Y AF47 AH03 AH12 BA01 BB06 BC01 BC06 4H028 AA10 AA11 AA28 AA30 AA35 AA38 AA44 BA06 4J001 DA03 DA04 DB01 DB02 DB05 DC03 DC05 DD01 EA02 EA06 EA08 EA14 EA15 EA16 EA17 EB08 EB09 EB10 EB14 EB34 EB36 EB37 EB71 EC05 EC07 EC08 EC09 EC13 EC16 EC43 EC85 ED63 ED66 EE08E EE23E EE55E EE64E EE75E FA03 FA06 FB03 FC03 FD01 GA13 GB13 GB14 HA02 JA07 JA12 JB01 JB13 JB19 JB31 JB32 CL04 CH2 CL08 DE0 CH2 CL04 DE2 87 DE147 EB137 EJ057 ER006 ET017 EU027 EU187 EW048 EW158 FD134 FD137 FD138 GL00 GQ00 GQ01

Claims (19)

[Claims] 1. A flame-retardant resin composition containing a thermoplastic resin polyamide elastomer resin composition and a flame retardant, wherein the thermoplastic polyamide elastomer resin composition comprises:
(a) thermoplastic polyamide elastomer resin, and (b) (b
-1) (b-1-1) a monocarboxylic acid having 7 to 23 carbon atoms and / or (b-1-2) a monoamine having 7 to 22 carbon atoms,
(b-2) (b-2-1) an aminocarboxylic acid having 6 or more carbon atoms,
(b-2-2) lactam having 6 or more carbon atoms, (b-2-3) diamine having 2 to 12 carbon atoms, and (b-2-4) 6 to 2 carbon atoms
2 obtained by reacting with one or more amide-forming monomers or amide-forming monomers selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids or aromatic dicarboxylic acids and their ester derivatives. The amide compound is a compound having a molecular end capped with a hydrocarbon group having 7 to 22 carbon atoms and having 3 or more amide bonds in the molecule, and has an average molecular weight of 600 to A flame-retardant resin composition containing a crystalline amide compound in the range of 1800. 2. The crystalline amide compound (b) is (b-1)
(b-1-1) Monocarboxylic acid having 7 to 23 carbon atoms and /
Or (b-1-2) a monoamine having 7 to 22 carbon atoms, and (b-
2) A crystalline amide compound obtained by a condensation reaction with (b-2-1) an aminocarboxylic acid having 6 or more carbon atoms and / or (b-2-2) a lactam having 6 or more carbon atoms. Item 1
The flame-retardant resin composition described. 3. The crystalline amide compound (b) is (b-1)
(b-1-1) Monocarboxylic acid having 7 to 23 carbon atoms and /
Or (b-1-2) a monoamine having 7 to 22 carbon atoms, and (b-
2) (b-2-3) a diamine having 2 to 12 carbon atoms, and (b-2-4)
The flame-retardant resin according to claim 1, which is a crystalline amide compound obtained by a condensation reaction with an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an alicyclic dicarboxylic acid or an aromatic dicarboxylic acid, and an ester derivative thereof. Composition. 4. The thermoplastic polyamide elastomer resin composition is the thermoplastic polyamide elastomer resin.
The flame-retardant resin according to claim 1, which is a thermoplastic polyamide elastomer resin composition in which (a) is further blended with a carbodiimide compound (c) or a carbodiimide compound (c) and a phenoxy resin (d). Composition. 5. The thermoplastic polyamide elastomer resin (a) obtained by copolymerizing (a-1) a polyamide oligomer having a carboxyl group and / or an amino group at the terminal group with (a-2) a polyether polyester. Which is a thermoplastic polyether ester amide block copolymer, wherein the polyamide oligomer having a carboxyl group and / or an amino group in the terminal group is (a-1-1) an aminocarboxylic acid having 6 or more carbon atoms, -1-2) lactam having 6 or more carbon atoms, (a-1-3) diamine having 2 to 12 carbon atoms, (a-1-
4) Aliphatic dicarboxylic acid having 6 to 12 carbon atoms, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and ester derivatives thereof, and (a-1-5) dimer acid having 20 to 48 carbon atoms and ester thereof 1 selected from the group consisting of derivatives
Or two or more polyamide-forming monomers or polyamide-formable monomers, and one or more polyamides selected so that the resulting polyamide oligomer has a carboxyl group and / or an amino group at its end. A polyamide oligomer having a terminal group terminated with at least one kind of a carboxyl group and / or an amino group, which is obtained by subjecting a combination of a forming monomer or a polyamide-forming monomer to a polyamidation reaction, and the polyether polyester is , (A-2-1) (a-2-1-1)
Aliphatic dicarboxylic acid having 6 to 12 carbon atoms, alicyclic dicarboxylic acid or aromatic dicarboxylic acid, (a-2-1-2) dimer acid having 20 to 48 carbon atoms, and (a-2-1- 3) Above (a-2-1
-1) and one or more polybasic acids selected from the group consisting of polybasic acids described in (a-2-1-2) and ester derivatives of polybasic acids and / or esters thereof. A derivative,
(a-2-2) (a-2-2-1) polyoxyalkylene glycol,
(a-2-2-2) Aromatic ring-containing polyether diol, and (a-2
-2-3) A polyhydric alcohol described in (a-2-2-1) and / or a polyhydric alcohol described in (a-2-2-2) and α, ω-dihydroxy hydrocarbon A poly (alcohol) obtained by an esterification reaction or a transesterification reaction with one or more polyhydric alcohols selected from the group consisting of a mixture and a polyhydric alcohol having a number average molecular weight in the range of 800 to 3000. The flame-retardant resin composition according to any one of claims 1 to 4, which is an ether polyester. 6. The thermoplastic polyamide elastomer resin (a) according to claim 5, wherein the terminal has a carboxyl group and / or
Or a polyamide oligomer having an amino group (a-1),
General formula (1) (In the formula, R ₁ represents a residue of a substituted or unsubstituted aliphatic dicarboxylic acid having 2 to 54 carbon atoms or a residue of a diol selected from one kind or a mixture of two or more kinds of alicyclic diols. R ₂ is a dicarboxylic acid residue and / or 20 to 20 carbon atoms selected from one or a mixture of two or more aliphatic dicarboxylic acids or aromatic dicarboxylic acids having 6 to 22 carbon atoms.
It represents the residue of a polymerized fatty acid selected from 48 dimer acids and one or a mixture of two or more of these derivatives. ) And has a number average molecular weight of 80.
The flame retardant resin composition according to any one of claims 1 to 5, which is a polyesteramide block copolymer obtained by copolymerization with a polyester (a-3) in the range of 0 to 3000. 7. R ₁ in the general formula (1) is a residue of at least one substituted or unsubstituted aliphatic diol having 2 to 12 carbon atoms and / or a residue of an alicyclic diol, The flame-retardant resin composition according to claim 6, wherein R ₂ is a residue of a dimer acid having 20 to 48 carbon atoms and / or an ester derivative thereof. 8. R ₁ in the general formula (1) is a residue of a dimer diol derived from a dimer acid having 20 to 48 carbon atoms, and R ₂ is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms. The flame-retardant resin composition according to claim 6, which is a residue, an aromatic dicarboxylic acid residue and / or a residue of an ester derivative thereof. 9. The thermoplastic polyamide elastomer resin has 20 carbon atoms in the constituent components of the elastomer.
The flame-retardant resin composition according to any one of claims 1 to 8, which contains 5% by weight or more of a unit derived from a component consisting of dimer acid of 48 to 48 and / or a derivative thereof. 10. The crystalline amide compound has a molecular terminal blocked with a saturated aliphatic hydrocarbon group having 7 to 22 carbon atoms, and has 6 to 6 carbon atoms through at least 3 or more amide bonds. The flame-retardant resin composition according to any one of claims 1 to 9, which has a structure in which 22 saturated aliphatic hydrocarbon chains are linked. 11. The blending ratio of the crystalline amide compound to the thermoplastic polyamide elastomer resin is 0.
The flame-retardant resin composition according to any one of claims 1 to 10, which is in a range of 1 to 20 parts by weight. 12. The flame retardant resin composition according to claim 1, wherein the flame retardant is a flame retardant selected from the group consisting of a metal hydroxide and a compound having a nitrogen atom. 13. The flame-retardant resin composition according to claim 12, wherein the metal hydroxide is magnesium hydroxide. 14. The flame-retardant resin composition according to claim 12, wherein the compound having a nitrogen atom is melamine cyanurate. 15. The use ratio of the thermoplastic polyamide elastomer resin composition and the flame retardant is 9 by weight.
The flame-retardant resin composition according to any one of claims 1 to 14, which is in a range of 8: 2 to 20:80. 16. The flame-retardant resin composition according to any one of claims 12 to 15, which further contains, as the flame-retardant, a flame-retardant composed of a compound having a phosphorus atom in the molecule. 17. The flame retardant comprising a compound having a phosphorus atom is at least one flame retardant selected from the group consisting of condensed phosphates, orthophosphates or dimers of orthophosphates. 16. The flame-retardant resin composition according to 16. 18. The surface electric resistance of the molded body made of the flame-retardant resin composition is 10 ¹³ Ω or less.
The flame-retardant resin composition according to any one of 1. 19. A molded product obtained by molding the flame-retardant resin composition according to any one of claims 1 to 18.