KR20120056477A - A nonhalogen flame retardant polyester resin composition - Google Patents

Abstract

PURPOSE: A halogen-free flame-retardant polyester resin compostion is provided to have high flame retardance, not to generate halogen based gas at combustion, and to have excellent processability, workability, physical properties, and thermal resistance. CONSTITUTION: A halogen-free flame-retardant polyester resin compostion comprises 50-78 weight% of polyester resin, 5-10 weight% of phosphinate or diphosphinate, 1-5 weight% of a nitrous flame retardance synergist, 15-30 weight% of an inorganic filler. The inherent viscosity of the polyester resin is 0.45-1 dl/g. The phosphinate and diphosphinate is in chemical formula 1 or chemical formula 2. The aramid based flame retardance synergist is meta-aramid fiber.

Description

A nonhalogen flame retardant polyester resin composition

The present invention relates to a polyester resin composition having excellent flame retardancy and heat resistance, and more particularly, to an inorganic filler including a non-halogen-based flame retardant, a nitrogen-based and aramid-based flame retardant, and providing strength, heat resistance and dimensional stability. The present invention relates to a polyester resin composition that is environmentally friendly and excellent in flame retardancy and heat resistance.

In general, polyester resins have excellent mechanical and electrical properties and physical and chemical properties, and are being applied to a wide range of fields such as automobiles, electrical and electronic devices, and office equipment. In particular, polyethylene terephthalate resin is widely used as a variety of composite materials used in automobiles, electrical and electronic parts, etc. because of its excellent economical and heat resistance, chemical resistance, electrical properties, mechanical strength, and molding processability, and its usage is increasing.

When inorganic fillers, such as glass fiber, talc, mica, layered silicate, are added to polyester resin. Mechanical properties such as tensile strength, flexural strength and heat resistance are greatly improved, and thus may be used for more various applications. However, many applications also require high heat resistance and flame retardancy at the same time. Accordingly, development for imparting flame retardance to polyester resins has been progressed in various ways.

Polyester resins have been imparted with flame retardant properties by separately adding organic halogen-based flame retardants or auxiliary flame retardants in fields requiring flame retardancy because of their ability to burn well. However, halogen-based flame retardants containing chlorine or bromine element cause various problems such as corrosion of the processing equipment and resin decomposition by hydrogen halide. In addition, toxic gases caused by a large amount of halogenated compounds generated during combustion cause considerable life and property damage. In addition, a method of reducing the calorific value by adding an inorganic material such as aluminum hydroxide to the resin, and a method of adding a nitrogen-based flame retardant such as phosphorus or ammonium phosphate such as red to the resin are mainly used, but limitations in terms of the flame retardant effect and processability Has been shown.

Meanwhile, some European countries have proposed restrictions on the use of flame retardants, such as polybrominated biphenyls (PBBs) and polybrominated biphenylethers (PBDEs), due to fears of dioxin generation during fire and incineration. In addition, due to the environmental safety evaluation in automotive and electrical and electronic components, there have been attempts to strictly limit the use of harmful heavy metals and bromine-based flame retardants and antimony compounds.

Due to such movements, the necessity of developing technologies for non-halogen flame retardants is urgently needed. In particular, in the case of the fuser housing used in the printer, the structure of the molded article is very fine and complicated, requiring high resin flow characteristics and processability, and also requiring high heat resistance and flame resistance due to high temperature and high temperature environment. Since the paper discharged through the direct contact with the user has a characteristic that there is a demand for the development of non-halogen flame-retardant polyester material without the emission of toxic substances in the high temperature, high temperature environment.

Such non-halogen-based flame retardant polyester resins are described in Japanese Patent Laid-Open Publication No. 1999-209587, organophosphorus-based flame retardants and cyanuric acid adducts are added to thermoplastic polyester resins, and glass fibers and inorganic fillers are used for halogen. Disclosed is a flame retardant composition that is not used, but in this case, there is a disadvantage in that the viscosity of the resin composition and the mechanical strength of the molded article decrease in using a large amount of phosphorus-based flame retardant.

In addition, Korean Patent Publication No. 2009-0030505 discloses a method of adding layered silicate and inorganic activator to phosphorus-based flame retardant and nitrogen-based flame retardant to impart flame retardancy and heat resistance, but has a deterioration in mechanical rigidity and heat resistance of the composition. There are restrictions that come.

Therefore, in order to impart flame retardancy in the above-described prior art, a large amount of flame retardant is required, which causes disadvantages of excessive cost increase, physical property deterioration, heat resistance deterioration, and electrical property deterioration.

Accordingly, the present inventors have conducted research to solve the above problems, and as a result, by including an inorganic filler that includes a non-halogen-based flame retardant, nitrogen-based and aramid-based flame-retardant synergists, and imparts strength, heat resistance and dimensional stability, The present invention was completed by confirming that a polyester resin composition which is friendly and excellent in flame retardancy and heat resistance can be prepared.

Accordingly, an object of the present invention is to provide a polyester resin composition that complements the above technical disadvantages and reduces flame retardant content and thereby realizes effective flame retardancy with excellent mechanical rigidity and heat resistance. Further, another object of the present invention is to provide a molded article produced using the polyester resin composition of the present invention.

In order to achieve the above object, the present invention

(A) 50 to 78% by weight of polyester resin,

(B) 5-10% by weight of phosphinates or diphosphinates,

(C) 1 to 5% by weight of nitrogen-based flame retardant,

(D) 1 to 3% by weight of an aramid flame retardant, and

(E) 15-30 wt% of inorganic filler

It provides a non-halogen flame-retardant polyester resin composition comprising a.

In the following the invention is explained in more detail.

(A) polyester resin

The polyester resin of the present invention consists of at least one aromatic, aliphatic, or alicyclic dicarboxylic acid compound and at least one aliphatic or alicyclic glycol moiety. Preferably the aromatic dicarboxylic acid consists of 6 to 20 carbon atoms and the aliphatic or cycloaliphatic dicarboxylic acid consists of 3 to 20 carbon atoms. Aliphatic or cycloaliphatic glycols consist of 2 to 20 carbon atoms. Preferably, at least one of polyethylene terephthalate resin, polypropylene terephthalate resin or polybutylene terephthalate resin may be selected and used, and more preferably polyethylene terephthalate may be used.

Polyester resin can be synthesize | combined using a dicarboxylic acid compound and a glycol compound. Processes for preparing polyester resins using dicarboxylic acids and glycol compounds usually proceed in two stages: ester reactions and polycondensation reactions, the progress of which is well known in the art.

Dicarboxylic acid compounds that can be used in the present invention include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, seba Acid, 1,4-, 1,5-, 2,3-, 2,6-, or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or 4,4 ' Dibenzyldi carboxylic acid and the like, but not limited thereto, and preferred dicarboxylic acid compounds are terephthalic acid, isophthalic acid or mixtures thereof.

Glycol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1, 2-, 1,3-, or 1,4-cyclohexanedimethanol, neopentyl glycol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the like, but are not limited thereto. The glycol compound is ethylene glycol, cyclohexanedimethanol or mixtures thereof.

In consideration of the processability and mechanical properties of the polyester resin, it is preferable to use an IV of 0.45 to 1 dl / g, and most preferably 0.5 to 0.8 dl / g.

The amount of the polyester resin is preferably 50 to 78% by weight of the total resin composition. When the content of the polyester resin is less than 50% by weight, the amount of the resin is small compared to the content of the flame retardant and the inorganic filler, which greatly increases the efficiency of workability during feeding and extrusion, and also protrudes the inorganic filler into the appearance of the molded article. This is because the likelihood of appearance defects is significantly increased. In addition, when the content is more than 78% by weight, the solidification rate is slowed productivity is reduced, there may be a problem that the dimensional instability due to post-deformation is relatively large.

(B) Phosphinates  And Diphosphinate  compound

In the present invention, as the non-halogen-based flame retardant, phosphinates or diphosphinates represented by the following general formula (1) or (2) are used:

<Formula 1>

<Formula 2>

Wherein R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ represents a linear or branched C ₁ -C ₁₀ alkylene, arylene, alkylarylene Or arylalkylene, M is a metal such as calcium, magnesium, zinc or aluminum, m is 2 or 3, n is 1 or 3, and X is 1 or 2.

In the present invention, they may be used independently of each other, or may be used in a mixture of two or more different kinds. In the present invention, phosphinate or diphosphinate is preferably used at 5 to 10% by weight of the total resin composition as described above. If the content of the flame retardant is less than 5% by weight, flame retardancy at various thicknesses (0.8mm or 1.6mm) is difficult to be effectively given. If the content of the flame retardant is more than 10% by weight, it is not only disadvantageous in terms of cost but also injection and molding during extrusion and injection. Can cause a significant disadvantage in processability and also cause a decrease in mechanical properties such as heat deformation temperature and tensile strength due to an increase in flame retardant content.

The resin composition of the present invention is environmentally friendly because it does not generate a halogen gas during processing by using phosphinate or diphosphinate as a flame retardant, and mechanical and thermal properties due to a synergy effect with the aramid flame retardant mentioned below. The effect can be minimized.

(C) nitrogen-based flame retardant Synergist

In the present invention, a nitrogen-based flame retardant increasing agent or a nitrogen-containing flame retardant increasing agent may be used.

As the nitrogen-containing flame retardant, a compound having a triazine structure may be used, such as melamine, melamine cyanurate, triphenyl isocyanurate, and the nitrogen-phosphorus-containing flame retardant may include melamine phosphate, melamine pyrophosphate, and ammonium polyphosphate. , Alkylamine phosphates, piperidine acid polyphosphates, and the like, and these may be used alone or in combination.

In addition, various nitrogen-based flame retardants and / or intumescent additives (eg, polyhydric compounds such as dipentaerythritol, starch, dextrin, inorganic acids, etc.) may be used alone or in combination of two or more.

The amount of the nitrogen-based flame retardant increasing agent is preferably 1 to 5% by weight in the total resin composition. When less than 1% by weight of nitrogen-based flame retardant is added, it is difficult to realize the flame retardancy of the resin due to the small synergy effect with the flame retardant, and when it exceeds 5% by weight, it is not only disadvantageous in terms of cost, but also during injection and injection. It may cause a great disadvantage in processability in molding and may cause a decrease in mechanical properties such as heat deformation temperature and tensile strength.

(D) Aramid system  Flame Retardant Synergist

In the present invention, aramid-based flame retardant may be used meta-aramid fibers. Metaaramid fiber may be represented by the following formula (3).

Formula 3

Meta aramid fibers can be obtained by polymerization of meta-substituted aromatic diacid chlorides and diamines, and have very high heat resistance (pyrolysis at about 370 ^° C.), and the basic properties of the fibers are poly Similar to esters, it is easy to process and is widely used in many fields as protective clothing and construction materials such as electrical insulating paper, fire fighting clothing, and Hanbok, which require heat and flame resistance. The meta-aramid fiber is in the chopped state, and considering the processability and dispersibility of the polyethylene terephthalate resin, the length is preferably 1.5-2mm, the diameter is 3-5㎛.

In the present invention, the content of the aramid flame retardant is preferably 1 to 3% by weight based on the total polyester resin composition. When the content of the aramid-based flame retardant is less than 1% by weight, the effect as a flame retardant synergist is significantly lowered, when the content of more than 3% by weight may result in workability and surface defects of the molded article.

The meta-aramid fiber used as the aramid flame retardant in the present invention is to reduce the amount of the phosphinate or diphosphinate flame retardant and nitrogen-based flame retardant, while imparting more than equal flame retardant properties to the polyester resin composition, and At the same time, mechanical and thermal properties and processability due to flame retardant reduction can improve the appearance characteristics of the molded article.

(E) Inorganic filler

In the present invention, the inorganic filler of component (E) is used for improving heat resistance and mechanical strength, processability and moldability, and such inorganic filler is typically glass fiber. As the glass fiber, a conventional chopped strand may be used, and a coupling agent may be used to increase adhesion to the resin.

In consideration of the processability and mechanical properties of the polyester resin composition, the diameter of the glass fiber is preferably chopped to 8 µm to 18 µm and 2 mm to 7 mm in length. Other inorganic fillers that can be used are at least one selected from the group consisting of carbon fiber, glass beads, glass flakes, clay, kaolin, talc, mica, calcium carbonate, and barium sulfate.

The content of the inorganic filler is 15 to 30% by weight based on the total polyester resin composition. When the content of the inorganic filler is less than 15% by weight, the mechanical stiffness and heat resistance are reduced, the effect is insignificant, and when the content of the inorganic filler exceeds 30% by weight, workability and moldability are remarkably deteriorated.

(F) Other additives

On the other hand, the resin composition of the present invention may further include an additive for various purposes, the kind and content thereof is according to those skilled in the art. For example, lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, mold release agents, pigments, antistatic agents, conductivity giving agents, magnetic imparting agents, crosslinking agents, antimicrobial agents, processing aids, anti-friction agents, anti-wear agents and coupling agents, alone or in combination It may include.

At this time, the total amount of the other additive components is preferably used in about 0.2 to 5.0% by weight relative to 100% by weight of the resin composition, it is obvious that the present invention is not necessarily limited thereto.

The polyester resin composition of the present invention is kneaded and extruded with a twin screw melt kneading extruder at a temperature of 230 to 270 ° C. by a commonly used blending method to produce pellets for molding, and the pellets are hot air at 100 to 120 ° C. for at least 4 hours. After drying, it can be produced by molding with an injection molding machine. As such, the resin composition and the molded article using the same according to the present invention are excellent in flame retardancy and heat resistance, and can be used for various purposes.

The non-halogen flame retardant polyester resin composition according to the present invention comprises a polyester resin, a flame retardant imparting flame retardancy, a nitrogen flame retardant elevating agent and an aramid flame retardant elevating agent, and an inorganic imparting strength, heat resistance and dimensional stability It will contain a filler. The non-halogen flame-retardant polyester resin composition invented as described above has high flame retardancy and does not generate halogen-based gas during combustion, and also has excellent processability, moldability, mechanical properties and heat resistance. Electronic components, office equipment, in particular, such as the housing of the printer fuser that requires high thermal stability can be usefully used in various applications.

Hereinafter, the present invention will be described in more detail by describing preferred embodiments of the present invention, and comparative examples and experimental examples for comparison thereto. However, the present invention is not limited to the following Examples and Experimental Examples, and various forms of embodiments can be implemented within the scope of the appended claims, and only the following examples are provided in the art to complete the present disclosure. It is intended to facilitate the practice of the invention to those skilled in the art.

Example  1-7 and Comparative example  1-7

The raw materials were well mixed in a Henschel mixer with the composition components and contents shown in Tables 1 (Examples 1 to 7) and Table 2 (Comparative Examples 1 to 7) to be uniformly dispersed, and then L / D = 40, f = Extrusion at a temperature of 230 ~ 270 ℃ by biaxial melt kneading extruder of 25mm manufactured in pellet form, hot air dried at 100 ~ 120 ℃ for 4 hours, injection molding at a temperature of 230 ~ 270 ℃ to mold the specimen Example 1 To 7 and the resin compositions of Comparative Examples 1 to 7 were prepared. Glass fiber and arimid flame retardant synergist was fed through the extruder intermediate point.

Composition (% by weight) Example One 2 3 4 5 6 7 Polyester resin 58.8 58.8 59.6 62.4 55.2 77.4 66.4 Flame retardant 7.2 7.2 6.4 5.6 6.8 5.6 5.6 Nitrogen-based flame retardant 3 One 3 One 5 One 5 Aramid Flame Retardant One 3 One One 3 One 3 Inorganic filler 30 30 30 30 30 15 20

Composition (% by weight) Comparative example One 2 3 4 5 6 7 Polyester resin 59 56.2 62.6 62.4 58.4 78.4 69.4 Flame retardant 8 8.8 6.4 5.6 5.6 5.6 5.6 Nitrogen-based flame retardant 3 5 One 2 One One 5 Aramid Flame Retardant - - - - 5 - - Inorganic filler 30 30 30 30 30 15 20

The specification of the material used in the present Example and the comparative example is as follows.

(A) Polyester resin: polyethylene terephthalate (high viscosity: 0.80 dl / g (25 ° C., in 50/50 solution of phenol / tetrachloroethane))

(B) Flame Retardant (Phosphate): Clariant's aluminum diethylphosphinate (OP1240)

(C) Nitrogen-based flame retardant: melamine polyphosphate from Ciba (Melapur 200/70)

(D) Aramid flame retardant: Meta aramid fiber (METAone) from Huvis (bolted to 1.5 mm)

(E) Inorganic filler: KCC's glass fiber CS 321 (3mm bolted)

Physical properties of the specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Tables 4 and 5 below.

(1) Tensile strength and tensile elongation: It evaluated based on ASTMD638.

(2) Heat deflection temperature (HDT): evaluated under a load of 18.6kgf / cm ² in accordance with ASTM D648.

(3) Impact strength: evaluated according to ASTM D256 (1/8 inch thick, notched Izod).

(4) Flame retardancy: Measured according to UL94 test method defined by Underwriter's Laboratory Inc. of the United States, after 10 seconds of flaming of the burner on a vertically maintained specimen of a certain size It is a method of evaluating flame retardancy from the afterflaming time and drip property. Afterflaming time is the length of time that the specimen continues flame burning after the ignition source is far away. Determined by complexing, and the degree of flame retardancy is divided according to Table 3 below.

division V2 V1 V0 HB Residual flame time of each sample 30 seconds or less 30 seconds or less Less than 10 seconds Flame retardant 5 Total residue time of the sample 250 seconds or less 250 seconds or less 50 seconds or less Ignition of cotton by drip has exist none none

(5) Surface characteristics of the appearance: 3 mm thick specimens were injection molded, and it was visually judged whether the glass fibers protruded from the surface. Grade).

As shown in Tables 4 and 5, the polyester resin compositions of Examples 1 to 4 according to the present invention have a high tensile strength and heat deformation temperature as compared with Comparative Examples 1 to 4, which do not contain an aramid flame retardant. It maintains excellent surface condition and flame retardancy while maintaining. In Comparative Example 5, in which an excess of aramid-based flame retardant is included, the mechanical properties and flame retardance are not relatively reduced, but the prominent inorganic filler and gas protruding shapes appear on the exterior end of the molded article, indicating that the surface state of the exterior is reduced. Can be. Examples 6 to 7 and Comparative Examples 6 to 7 show a change when the inorganic filler is reduced in the same composition, which is also the same as that of Examples 1 to 4 and Comparative Examples 1 to 4. If it is not included it can be seen that the flame retardancy is significantly reduced.

Properties Example One 2 3 4 5 6 7 Tensile strength (kgf / cm) 847 805 888 914 893 534 647 Elongation (%) 0.8 One 1.3 1.6 1.4 1.7 1.5 Heat deformation temperature (캜) 215 216 218 221 214 212 216 Impact Strength (kgfcm / cm) 1.6 2 3.4 3.6 2.2 1.4 1.8 Flame retardant (0.8 mm thick) V0 V0 V0 V0 V0 V0 V0 Flame retardant (1.6 mm thick) V0 V0 V0 V0 V0 V0 V0 Surface characteristics of the appearance ㅇ ㅇ ㅇ ㅇ ㅇ ㅇ ㅇ

Properties Comparative example One 2 3 4 5 6 7 Tensile strength (kgf / cm) 724 662 841 954 824 557 669 Elongation (%) 0.4 0.4 1.2 1.7 1.3 1.4 1.2 Heat deformation temperature (캜) 206 204 218 223 215 213 218 Impact Strength (kgfcm / cm) 1.4 1.2 3.4 3.5 2.8 1.7 2.2 Flame retardant (0.8 mm thick) V0 V0 V1 V2 V0 V2 V2 Flame retardant (1.6 mm thick) V0 V0 V0 V1 V0 V1 V1 Surface characteristics of the appearance X x o o x ㅇ ㅇ

Claims (7)

(A) 50 to 78% by weight of polyester resin,
(B) 5-10% by weight of phosphinates or diphosphinates,
(C) 1 to 5% by weight of nitrogen-based flame retardant,
(D) 1 to 3% by weight of an aramid flame retardant, and
(E) Non-halogen flame-retardant polyester resin composition containing 15-30 weight% of inorganic fillers. The non-halogen flame retardant polyester resin composition according to claim 1, wherein the polyester resin has an intrinsic viscosity (IV) of 0.45 to 1 dl / g. The non-halogen flame retardant polyester resin composition according to claim 1, wherein the phosphinate salt or diphosphinate salt is represented by the following Chemical Formula 1 or 2.
Formula 1

(2)

In Formulas 1 and 2, R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ represents a linear or branched C ₁ -C ₁₀ alkylene, arylene, Alkylarylene or arylalkylene, M is calcium, magnesium, zinc or aluminum, m is 2 or 3, n is 1 or 3, and X is 1 or 2. The group of claim 1, wherein the nitrogen-containing flame retardant synergist is a group consisting of melamine, melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkylamine phosphate and piperidine acid polyphosphate. Non-halogen flame-retardant polyester resin composition, characterized in that at least one selected from. The non-halogen flame retardant polyester resin composition according to claim 1, wherein the aramid flame retardant synergist is meta aramid fiber. The non-halogen-based egg according to claim 1, wherein the inorganic filler is at least one selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, clay, kaolin, talc, mica, calcium carbonate and barium sulfate. Softened polyester resin composition. Molded article manufactured using the polyester resin composition according to claim 1.