JP2000290480A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonhalogen flame-retardant resin composition having excellent tensile elongation. SOLUTION: This composition is obtained by formulating 100 pts.wt. of a thermoplastic copolyester resin prepared form (a) 70-99.5 mol% of terephthalic acid or its ester forming derivative and (b) 0.5-30 mol% of a dimer acid or its ester forming derivative as acid components and 1,4-butanediol as a glycol component with 6-100 pts.wt. of a triazine compound. The dimer acid contains >=10 wt.% of a chain dimer acid shown by the general formula (R is an alkyl group; the sum of number of carbons of Rm, Rn, Rp and Rq is 31) and has <=10 gI/100 g iodine value, <=1 wt.% monomer acid contained in the chain dimer acid and <=1 wt.% trimer acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a non-halogen flame-retardant resin composition having excellent tensile elongation.

[0002]

2. Description of the Related Art Thermoplastic polyester resins such as polybutylene terephthalate have high moldability, mechanical properties,
As a molding material having excellent electrical properties, it is widely used in mechanical parts, electric / electronic parts, automobile parts and the like. on the other hand,
In these application fields, particularly in electric and electronic parts, flame retardancy is required. Currently, a combination system of a halogen flame retardant such as a bromine flame retardant and a chlorine flame retardant and an inorganic flame retardant such as antimony oxide is used. Is used. However, starting from recent environmental problems, there has been an increasing demand for resin materials that do not contain halogen-based flame retardants, mainly in Europe.

Hitherto, in order to solve such a problem, a method of adding a phosphoric ester compound or red phosphorus has been known (for example, JP-A-49-103951).

However, when a phosphoric acid ester is used, if it is added in a large amount in order to impart sufficient flame retardancy, the surface of pellets obtained by kneading and extruding the flame retardant due to the low compatibility with the polyester resin. Bleed out occurs. When red phosphorus is used, the danger of the red phosphorus powder itself and the color of the resin composition obtained by kneading and extruding cannot avoid a red color. In addition, the mechanical properties of the resin composition containing any of the flame retardants, particularly the tensile elongation at break, are small and cannot be put to practical use.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a flame-retardant resin composition containing no halogen and having excellent tensile elongation. is there.

[0006]

The object of the present invention is to provide (a) terephthalic acid or its ester-forming derivative 70 to 99.5;
Mol%, and (b) 0.5 to 30 mol% of dimer acid or its ester-forming derivative as an acid component, and 100 parts by weight of a thermoplastic copolymer polyester resin obtained with 1,4-butanediol as a glycol component. , A triazine compound in an amount of 6 to 100 parts by weight, wherein the dimer acid has a general formula

Embedded image (Wherein R represents an alkyl group, and Rm, Rn, Rp and Rq
Has a chain dimer acid represented by the following formula: 10% by weight or more, an iodine value of 10 gI / 100 g or less, a monomeric acid contained in the dimer acid of 1% by weight or less, and a trimer. This is achieved by a thermoplastic resin composition characterized in that the acid content is 1% by weight or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic copolymer polyester resin used in the present invention comprises terephthalic acid and dimer acid as an acid component, and 1,4-butanediol as a glycol component.

It is essential that the terephthalic acid content in the acid component is 70 to 99.5 mol%, that is, the dimer acid content is 0.5 to 30 mol%, preferably the dimer acid content is 1 to 20 mol%. Especially preferably, it is 3 to 15 mol%.

Terephthalic acid in the acid component is less than 70 mol%,
That is, when the dimer acid content exceeds 30 mol%, the tensile strength is significantly reduced. On the other hand, terephthalic acid in the acid component is 99.
If it exceeds 5 mol%, that is, if the amount of dimer acid is less than 0.5 mol%, the tensile elongation is significantly reduced.

The raw material of dimer acid, one of the acid components of the thermoplastic polyester resin used in the present invention, is an unsaturated fatty acid having 18 carbon atoms or a lower alkyl ester thereof, for example, oleic acid, linoleic acid, linolenic acid. Acid, elaidic acid and the like. These are polymerized by a viscosity catalyst such as montmorillonite to obtain a mixture of a trimeric acid having 54 carbon atoms and a monomer acid having 18 carbon atoms in addition to the dimer acid having 36 carbon atoms. This mixture is subjected to vacuum distillation, molecular distillation and hydrogenation to obtain the dimer acid used in the present invention.

The dimer acid obtained has a chain form, an aromatic ring,
It is a mixture having each structure of an alicyclic monocyclic ring and an alicyclic polycyclic ring. When the content of linoleic acid, which is a raw material of dimer acid, is large, the chain structure decreases and the cyclic structure increases.

The dimer acid, which is one of the acid components of the thermoplastic polyester resin used in the present invention, has a general formula

Embedded image (Wherein R represents an alkyl group, and Rm, Rn, Rp and Rq
It is essential that the total number of carbon atoms of the linear dimer acid represented by the formula is 31% by weight or more.
12% by weight or more. When the chain dimer acid content is less than 10% by weight, the tensile elongation of the thermoplastic copolyester resin itself becomes poor, so that the tensile elongation of the composition of the present invention becomes poor.

It is important that the dimer acid, which is one of the acid components of the thermoplastic polyester resin used in the present invention, has an iodine value of 10 gI / 100 g or less. 10
If it exceeds gI / 100 g, the color of the thermoplastic copolyester resin becomes poor.

It is important that the monomeric acid contained in the dimer acid, which is one of the acid components of the thermoplastic copolyester resin used in the present invention, is 1% by weight or less, preferably 0.7% by weight or less. It is. If it exceeds 1% by weight, the condensation polymerization does not proceed sufficiently during the production of the thermoplastic copolyester resin, the viscosity does not rise sufficiently, and the tensile elongation of the obtained thermoplastic copolyester resin itself becomes poor. Therefore, the tensile elongation of the composition of the present invention is also poor.

It is important that the trimer acid contained in the dimer acid, which is one of the acid components of the thermoplastic polyester resin used in the present invention, is 1% by weight or less. When it exceeds 1% by weight, when the thermoplastic copolymer polyester resin and the triazine compound are melted and kneaded with a kneader or the like in the production of the resin composition of the present invention, the viscosity is increased so that the composition can be produced. Disappears.

Preferred examples of the dimer acid which is one of the acid components of the thermoplastic polyester resin used in the present invention include PRIPOL 100 manufactured by Unichema.
8, PRIPOL 1009, and even PRIPOL 1
008 as an ester-forming derivative of Uniquema
RIPLAST 3008, PRIPLAST 189 as an ester-forming derivative of PRIPOL 1009
9 is given.

It is important that the glycol component of the thermoplastic polyester resin used in the present invention is 1,4-butanediol.

The thermoplastic copolyester resin used in the present invention has a relative viscosity .eta.rel measured at 20.degree. C. using a mixed solvent of tetrachloroethane: phenol = 2: 3. It is preferably at least 6, and is preferably less than 3.0 from the viewpoint of melt fluidity.

The method for producing the thermoplastic copolymer polyester resin in the present invention is not particularly limited, and can be carried out according to a known method.

For example, terephthalic acid, dimer acid, 1,
A method in which 4-butanediol is directly or simultaneously esterified or transesterified and then polymerized can be employed. At the time of these polymerization or transesterification reactions, various known catalysts, stabilizers, modifiers or additives may be used.

The triazine compound used in the present invention includes a 2,4,6-triamino-1,3,5-triazine derivative having 3 to 50 carbon atoms and a nitrogen content of 20 to 80%, a cyanuric acid derivative and an isocyanuric acid derivative. Acid derivatives, specifically, for example, melamine, melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, and tris (3-hydroxy-N-propyl) isocyanurate.

In the present invention, it is important that the compounding amount of the triazine compound is 6 to 100 parts by weight based on 100 parts by weight of the thermoplastic copolymerized polyester resin.
0 to 70 parts by weight is preferred. If it exceeds 100 parts by weight, the tensile elongation is significantly reduced, and if it is less than 6 parts by weight,
Flame retardancy becomes insufficient.

Further, a non-halogen flame retardant such as phosphate ester, red phosphorus, zinc borate or the like which does not contradict the object of the present invention can be used in combination with the composition of the present invention.

The composition of the present invention may contain ordinary additives such as antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, thioethers, phosphites and the like) as long as the object of the present invention is not impaired. UV absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), crystal nucleating agents (eg, kaolin, talc, etc.), lubricants and mold release agents (eg, montanic acid and its salts,
Coloring agents including stearic acid and its salts, stearyl alcohol, stearyl amide, silicone resin, etc., dyes (eg, nitrosine, etc.) and pigments (eg, carbon black, cadmium sulfide, phthalocyanine, etc.), and additives (eg, silicone oil) ) Can be added.

Further, in addition to these, fiber fillers such as glass fibers, plate-like fillers such as mica and glass flakes, and spherical fillers such as glass beads may be contained. With such a filler, for example, mechanical properties and heat resistance can be improved.

The composition of the present invention may contain a polybutylene terephthalate resin. In this case, the amount of the dimer acid component is 0.5 to 3 based on the sum of the thermoplastic copolymerized polyester resin and the polybutylene terephthalate resin.
It must be set to be 0 mol%.

The composition of the present invention may contain a small amount of other thermoplastic resins (for example, olefin resins such as polyethylene, polypropylene, and ethylene copolymers, acrylic resins, fluororesins, polyamides) without impairing the object of the present invention. ,
Polyacetal, polycarbonate, polysulfone, polyphenylene oxide, polyester, ABS resin,
A graft copolymer such as MBS resin).

It is important that the thermoplastic copolyester resin and the triazine compound are sufficiently kneaded and dispersed in the composition of the present invention until it becomes a final molded article. As a method for this, for example, a pellet-shaped resin may be produced using a different-direction rotating twin-screw kneading extruder, and may be subjected to a molding step.

[0029]

The resin composition of the present invention relates to a non-halogen flame-retardant resin composition having excellent tensile strength, and is used for electric and electronic parts.

[0030]

Embodiments will be described below with reference to embodiments. The evaluation of physical properties was performed according to the following methods. Tensile strength, tensile elongation: ASTM D638 Combustion test: UL94 Vertical test Content of chain structure in dimer acid: J. Am. Oil. Chemist's
After performing the same treatment as described in Soc., Vol. 51, p. 522 (1974), analysis was performed by GS-MS. Content of monomeric acid and trimeric acid in dimer acid: JA
m. Oil. Chemist's Soc. 52, 81-page (1974
Year) according to the method described. Iodine value: ISO 3961

The dimer acid used in the present invention was produced by the above-mentioned method using linoleic acid or a mixture of linoleic acid and oleic acid as a starting material. The properties are shown in Table 1.

[0032]

[Table 1]

The thermoplastic copolyester resin used in the present invention was produced as follows. Dimethyl terephthalate, 24.3 kg of 1,4-butanediol, 5 g of tetra-n-butyl titanate and dimethyl terephthalate as transesterification catalysts were charged into a 100 L reactor with the composition shown in Table 2 at 40 ° C./hour. 21 at heating rate
Heat to 0 ° C, distill off the generated methanol out of the system,
A transesterification reaction was performed. After the methanol distillation was almost completed, 5 g of tetra-n-butyl titanate as an esterification catalyst and the dimer acid shown in Table 1 were added in the composition shown in Table 2, and the temperature was raised at a rate of 230 ° C./hour at 230 ° C.
C. to carry out an esterification reaction. Next, the reaction product was transferred to a polymerization machine, tetra-n-butyl titanate was added as a polymerization catalyst to the composition shown in Table 2, and the temperature was raised to 250 ° C. and the degree of vacuum to 0.5 mmHg over 1 hour.
Thereafter, polycondensation was performed for 3 hours. Table 2 also shows sample names and melting points of the obtained thermoplastic copolyester resins. TPE-2 stopped increasing in melt viscosity during the polycondensation step.

[0034]

[Table 2]

Examples 1 to 4 and Comparative Examples 1 to 7 20 parts by weight of a triazine compound (melamine cyanurate, manufactured by OMV Chemie) were blended with 100 parts by weight of the thermoplastic polyester resin obtained by the above-mentioned production method. After pre-mixing, the mixture was melt-kneaded with a 30 mm-diameter bi-directional rotary extruder to obtain pellets. In Comparative Example 2, the viscosity was remarkably increased during the melt-kneading, and pellets could not be collected. The pellet of Comparative Example 3 was remarkably brownish.
After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 3. The combustion test results were all V-2.

[0036]

[Table 3]

Examples 5 to 7 and Comparative Examples 8 and 9 The thermoplastic copolymer polyester resin sample A and the polybutylene terephthalate resin (PBT120 manufactured by Kanebo Gosen Co., Ltd.) obtained by the above-mentioned processes were blended in the composition shown in Table 4. Was mixed with zinc borate (manufactured by Tomita Pharmaceutical Co., Ltd., 2335) and the triazine compound used in the examples in the composition shown in Table 4. After premixing, the mixture was melted with a 30 mm-diameter bidirectional twin screw extruder. After kneading and mixing, pellets were obtained. After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 4.

[0038]

[Table 4]

The use of a thermoplastic copolymer polyester resin obtained by copolymerizing a dimer acid having a controlled monomer acid content, trimer acid content, iodine value and dimer acid content having a chain structure, and a triazine flame retardant. And a non-halogen flame-retardant resin composition having excellent tensile elongation.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takayoshi Kuwahara 4-1 Kanebocho, Hofu City, Yamaguchi Prefecture Inside Kanebo Goden Co., Ltd. (72) Inventor Masaki Yamamoto 4-1 4-1 Kanebocho, Hofu City, Yamaguchi Prefecture Kanebo God F-term in Sen Co., Ltd. (reference) 4J002 CF071 EU186 FD136 GQ00 4J029 AA03 AB07 AC02 AD01 AE01 BA05 CA09 CB06A CB07A CB11A CD04 CD07 KB02

Claims (1)

[Claims] 1. An acid component comprising (a) 70 to 99.5 mol% of terephthalic acid or its ester-forming derivative and (b) 0.5 to 30 mol% of dimer acid or its ester-forming derivative, Thermoplastic polyester resin 100 obtained by using 4-butanediol as a glycol component 100
6 to 100 parts by weight of a triazine compound is blended with respect to parts by weight, and the dimer acid has the general formula: (Wherein R represents an alkyl group, and Rm, Rn, Rp and Rq
Has a chain dimer acid content of 10% by weight or more, an iodine value of 10 gI / 100 g or less, and a monomeric acid contained in the dimer acid of 1% by weight or less. A thermoplastic resin composition comprising an acid of 1% by weight or less.