KR19980074179A - Non-halogen flame retardant thermoplastic resin composition excellent in heat resistance and processability - Google Patents

Abstract

The present invention is a poly (1,4-cyclohexylenedimethylene terephthalate) resin composition, reinforced with glass fiber and inorganic filler, melamine cyanurate as flame retardant, zinc borate and antimony trioxide as flame retardant aid Non-halogen-based flame retardant that has excellent mechanical properties and flame retardancy than halogen-based flame retardant, has excellent heat resistance without discoloration and deformation even above 260 ℃, and is harmless to human body because it uses non-halogen-based flame retardant. It relates to a resin composition.

Description

Non-halogen flame retardant thermoplastic resin composition excellent in heat resistance and processability

The present invention relates to a non-halogen flame-retardant thermoplastic resin composition, more specifically non-halogen to a resin mixed with a glass fiber reinforced resin and an inorganic filler of poly (1,4-cyclohexylenedimethylene terephthalate) (hereinafter referred to as PCT) It relates to a non-halogen-based flame retardant thermoplastic resin composition, which is excellent in thermal stability and processability by using a flame retardant and does not generate dioxin.

PCT is a crystalline polyester that has excellent mechanical properties, heat resistance, chemical resistance, durability at high temperature and high humidity, and in particular, dielectric breakdown strength and electrical properties are kept constant in the high temperature region. By using these characteristics, their use is expanding for electric and electronic parts and automobile parts requiring heat resistance. In addition, polybutylene terephthalate resin and polyethylene terephthalate resin, which have been used in the field of electric and electronic fields, cannot be applied to new fields such as surface mount technology requiring heat resistance of 260 ° C or higher. The use of PCT resins, which are advantageous in terms of cost, is increasing.

The PCT resin obtained by the polycondensation reaction can be used alone, but PCT resin composition which is endowed with flame retardancy, high rigidity and desired properties by adding glass fiber, inorganic fiber, flame retardant and various additives using single and twin screw extruders can be used. Mainly used.

In general, flame retardant components added to prevent fire or included in the structure are mainly halogen elements such as bromine and chlorine, and exhibit a flame retardant effect by releasing halogen gas contained in a fire. However, since flame retardants such as decabromodiphenyl oxide have a high possibility of generating carcinogens such as dioxins in a fire, activities are being banned in the European Union to prohibit the use of halogen flame retardants. Therefore, the activity of using a non-halogen flame retardant has increased greatly in recent years.

In polycarbonate / ABS blends, products using low molecular weight phosphorus-based flame retardants, such as triphenylene phosphate, have been developed early, and since the heat resistance is greatly reduced when using triphenylene phosphate, phosphorus having a large molecular weight has been tried in an effort to improve this problem. The development of flame retardants is active. In addition, products having been developed using, for example, ammonium phosphate, aluminum trihydrate, and the like have also been developed.

EP 174,493 discloses aromatic polycarbonates, styrene graft polymers such as acrylonitrile-butadiene-styrene copolymers and monophosphate esters such as triphenyl phosphate, tricresyl phosphate as flame retardants, halogen compounds and tetrafluoro Consists of ethylene However, monophosphate esters develop juicing on the surface during injection. In addition, in order to achieve UL 94 V-0 rating, it must be mixed with other flame retardants or added in a large amount, which leads to a decrease in heat distortion temperature.

EP 206,058 describes polymer mixtures containing polycarbonates, styrene maleic anhydride copolymers, alkyl- or aryl phosphates and mixtures of tetrafluoroethylene polymers and styrene containing graft polymers. This mixture also adds monophosphate esters as flame retardants and has the above disadvantages.

German Patent No. 2,921,325 describes a polymer mixture containing a diphosphate derived from aromatic polycarbonates and pentaerythritol. The phosphorus compound used in this mixture has the disadvantage of causing delamination due to low solubility.

In particular, when using such a monophosphate, the decomposition is severe at very high processing temperatures such as PCT, so the amount of use should be increased. In addition, since the physical property is severely reduced and easily becomes liquid, the extrusion processability is not good. Therefore, additional equipment is required for mass production.

An object of the present invention to improve the stability to the human body by using a non-halogen-based flame retardant excellent in processability to PCT reinforced resin, to provide a resin composition excellent in heat resistance and microwave resistance.

As a result of our efforts to achieve the above object, the present inventors have reinforced poly (1,4-cyclohexylenedimethylene terephthalate) resin with glass fiber, melamine cyanurate as flame retardant, zinc borate as flame retardant and By using antimony trioxide, mechanical properties and flame retardancy are superior to those of other non-halogen flame retardants, and have excellent heat resistance properties that do not cause discoloration and deformation even at temperatures above 260 ° C., thereby obtaining a non-halogen flame-retardant thermoplastic resin composition that is harmless to the human body. It was found out that the present invention was completed, and the present invention was completed.

Specifically, the composition of the present invention contains the following components.

(A) 15 to 55% by weight of PCT resin,

(B) 5 to 25% by weight of non-halogen flame retardant,

(C) 1 to 10% by weight of flame retardant aids, and

(D) 15 to 45% by weight of reinforcing agents.

The components of the composition are described in more detail as follows.

PCT resin as component (A) of the present invention is an aromatic polyester resin prepared by esterification or transesterification of a glycol with a difunctional carboxylic acid or its ester, followed by a polycondensation reaction of a low molecular weight product. Is 0.4 to 1.1, preferably 0.5 to 0.8, meaning poly (1,4-cyclohexylene dimethylene terephthalate). When the intrinsic viscosity is lower than the above range, the same physical properties as the composition in the present invention cannot be expected. When higher than the above range, there is a difficulty in processing. PCT resin of the present invention is represented by the following chemical structural formula.

[Formula 1]

As the above-mentioned glycol, 1,4-cyclohexanedimethanol (CHDM) is used as a main component, and 1,4-butanediol, 1,6-hexanehexane, 1,5-pentanediol, ethylene glycol, or 1, 3 -propanediol or the like may be used at 30 mol% or less, preferably 15 mol% or less of the total glycol component. It is hard to expect high heat resistance if it uses beyond the said range.

As the bifunctional carboxylic acid of the present invention, terephthalic acid or dimethyl terephthalate is used as a main component, dimethylisophthalate, isophthalic acid, succinic acid, adipic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalate, 2, 6-naphthalenedicarboxylic acid, dimethyl 2, 6-naphthalate, 1, 4-cyclohexanedicarboxylic acid, or the like may be used at 30 mol% or less of the total acid component.

PCT resin prepared by the above method may be transparent or opaque under the influence of the crystallization rate, and has a melting point of 260 to 300 ℃.

The amount of the PCT resin is 15 to 55% by weight based on the total resin composition, when less than the above range can not be expected to improve the physical properties, if more than the above range there is a risk of discoloration.

Flame retardant of component (B) of the present invention is a melamine cyanurate (C ₃ H ₆ N ₆ -C ₃ H ₃ N ₃ O ₃ ) and 1,3,5-triazine-2,4,6-trione and 1,3,5-triazine-2,4,6-triamine is mixed. The mixing ratio may be in the range of 0.2: 1 to 10: 1 or 1: 0.2 to 1:10, respectively, but 1: 1 to 2: 1 or 1: 1 to 1: 2 is preferable. This flame retardant has no melting point or softening point, and the volatilization temperature is 350 ° C. or higher, so it is thermally very stable. In addition, there is no halogen or hydrogen hydrogen even after combustion, which is not harmful to the human body. The amount of flame retardant is 5 to 25% by weight.

As the flame retardant adjuvant which is the component (C) of the present invention, zinc borate or antimony trioxide (Sb ₂ O ₃ ) is used alone or in a mixed state. The amount of flame retardant aid is 1 to 10% by weight. When zinc borate is used alone as a flame retardant aid, the amount of gas generated is smaller than that of antimony trioxide, but a large amount of zinc borate must be added to obtain flame retardancy. If the flame retardant aid is used in an amount of 5% by weight or more, the flame retardancy may be increased, but the impact strength may be decreased, so an appropriate amount is required.

15 to 45 weight% of glass fiber is used as a reinforcing agent of (D) component of this invention. The length of glass fiber is 2-8 mm, Preferably it is 3-5 mm. Thickness is 7-15 micrometers, Preferably it is 10-13 micrometers. Glass fibers may have various shapes such as spheres, mats, filaments, and long fibers, depending on the application. The smaller the thickness of the glass fiber, the better the physical properties. As the content of glass fiber increases, the strength in the weld decreases, so an appropriate content should be selected.

In addition to the said (A)-(D) component, an anti-dripping agent can be added. · Anti-dripping agent is an additive that prevents plastic from melting and separating when there is a flame on the plastic. It also helps flame retardant effect. Polytetrafluoroethylene is used as an anti-dripping agent, and the addition amount is 0.03-5 weight%. If the amount is less than the above range, there is little effect, and if it is large, the flow of resin is badly affected.

In addition, various inorganic fillers may be used alone or in combination. Examples include mica, talc, wollastonite, kaolin, barium sulfate, sodium carbonate and other inorganic fillers. Use of such inorganic fillers may increase mechanical rigidity and improve heat resistance. In addition, the use of antioxidants and heat stabilizers may help the heat resistance of the PCT resin, lubricants, colorants, etc. may be added.

The composition of this invention can be obtained by melt-processing said each component. The temperature of melt processing is 280-320 degreeC, and it can carry out by a single screw or twin screw extruder.

The present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited only to the following examples.

Example

The physical properties of the PCT prepared in Examples and Comparative Examples and the resin composition comprising the same were measured under the following conditions and methods.

1) Tensile strength: measured by ASTM D 638 (unit: kg / cm ² )

2) Flexural strength: measured by ASTM D 790 (unit: kg / cm ² )

3) Flexural modulus: measured by ASTM D 790 (unit: kg / cm ² )

4) Izod Impact Strength: Measures the impact strength at 1/4 in., 1/8 inch thick for specimens notched or notched according to ASTM D 256 (unit: kgcm / cm)

5) Flame retardant: Flame retardant is evaluated by UL 94.

6) Heat resistance: Test the degree of discoloration and deformation of the specimen by applying microwave and heat in a 1000 watt microwave oven.

7) Extrusion processability: Observe problems in the process of making chips or pellets by adding additives in the extruder.

Preparation Example (Manufacture of PCT Resin)

2910 g of dimethyl terephthalate, 1,4-cyclohexanedimethanol (trans / cis mixing ratio = 70/30), 3456 g, and 0.6 g of tetrabutyl titanate were added to the reactor, and the temperature was raised to 270 ° C. at atmospheric pressure to transesterify. Completed. The product was transferred to a polycondensation reactor and 1.5 g of tetrabutyl titanate was added, followed by 5.7 g of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as stabilizer Iganox 1010 (Shibagai Co., Ltd.). ) After adding 5.7 g, the polycondensation reaction was carried out for 100 minutes while gradually maintaining the vacuum degree below 0.3 Torr while increasing the reaction temperature to 305 ° C. Nitrogen was injected to disassemble the vacuum, and the polymer was ejected and cooled to obtain PCT. At this time, the intrinsic viscosity was 0.75 and the melting temperature was 289 ° C.

Example 1

45% by weight of PCT resin prepared in Preparation Example 1, 10% by weight of melamine cyanurate as flame retardant, 2, 3% by weight of zinc borate and antimony trioxide as flame retardant, glass fiber (LOC-492, LG Owens Co., Ltd.) Corning) 40% by weight was mixed and extruded to prepare chips (or pellets). The extruder used WP 40φ, where the resin temperature was 300 ° C. The chips thus prepared were dried at 100 ° C. for 4 hours, and then the specimens for physical properties were prepared with an injection capacity of 75 tons. The prepared specimens were left at 23 ° C. for 24 hours and subjected to no-load tests in the physical properties, flame retardancy, and microwave oven according to ASTM and UL 94 methods, and the results are shown in Table 3.

Example 2

The composition described in Table 1 was carried out in the same manner as in Example 1 and the results are shown in Table 3.

Comparative Examples 1 to 6

The composition described in Table 2 was carried out in the same manner as in Example 1 and the results are shown in Table 4.

TABLE 1

Example 1 Example 2 PCT 45 40 Melamine cyanurate 10 15 Zinc borate 3 2 Antimony trioxide 3 3 Fiberglass 40 40

TABLE 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PCT 40 40 40 40 40 45 Triphenyl phosphate 15 Melamine phosphate 15 Ammonium polyphosphate 15 Brominated phosphate 15 Brominated epoxy 15 Melamine cyanurate 10 Zinc borate 2 2 2 2 2 5 Antimony trioxide 3 3 3 3 3 Fiberglass 40 40 40 40 40 40

TABLE 3

division unit Example 1 Example 2 Mechanical Properties Tensile Strength Flexural Strength Flexural Modulus Izod Impact Strength 1/4 Notched 1/8 Notched Notched kg / cm ² kg / cm ² kg / cm ² kg.cm/cm 10001600140,0006329 11001700180,0007427 Flame retardant (2 mm) - V-O V-O Microwave no-load test deformation, expansion discoloration ⊙⊙ ⊙⊙ Extrusion Processability (290 ℃) ⊙ ⊙ ⊙ Excellent for preventing deformation, expansion and discoloration ○: Excellent for preventing deformation, expansion and discoloration ▲: Slight deformation, expansion and discoloration ×: Severe deformation, expansion and discoloration

TABLE 4

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Mechanical Properties Tensile Strength Flexural Strength Flexural Modulus Izod Impact Strength 1/4 Notched 1/8 Notched Notched 5301100123,0005197 10201740170,0006377 12502000143,00095410 10501620155,0007407 Flame retardant (2.0 mm) V-O V-O V-O V-1 Microwave no-load test deformation, expansion discoloration × ▲ ▲▲ ×× ⊙⊙ Extrusion Processability (290 ℃) ▲ × × ○ ⊙ ⊙ ⊙ Excellent for preventing deformation, expansion and discoloration ○: Excellent for preventing deformation, expansion and discoloration ▲: Slight deformation, expansion and discoloration ×: Severe deformation, expansion and discoloration

As can be seen in the above examples, the PCT resin composition of the present invention to which the melamine cyanurate flame retardant, zinc borate and antimony trioxide auxiliary flame retardant, and glass fiber is added, is more heat resistant and micro-resistant than other non-halogen-based PCT flame retardant resin compositions. The wave property is greatly improved, so that it is not deformed or discolored when used in the rotary ring of the microwave oven, and is excellent in heat resistance and workability.

Claims (10)

(A) 15 to 55% by weight of a poly (1,4-cyclohexylenedimethylene terephthalate) resin, (B) 5 to 25% by weight of non-halogen flame retardant, (C) 1 to 10% by weight of flame retardant aids, and (D) 15 to 45 weight% reinforcing agent Non-halogen flame retardant thermoplastic poly (1,4-cyclohexylenedimethylene terephthalate) resin composition containing The poly (1,4-cyclohexylenedimethylene terephthalate) resin of the component (A) is obtained by esterification or transesterification using a glycol and a bifunctional carboxylic acid or its ester as a raw material. An aromatic polyester resin produced by polycondensation reaction of a molecular weight product, wherein the composition is poly (1,4-cyclohexylene dimethylene terephthalate) having an intrinsic viscosity of 0.4 to 1.1. The composition of claim 2, wherein the glycol is a 1,4-cyclohexanedimethanol used as a main component. The group according to claim 2 or 3, wherein the glycol is composed of 1,4-butanediol, neopentylglycol, 1,6-hexanediol, 1,5-pentanediol, ethylene glycol, and 1,3-propanediol At least one component selected from is used in an amount of up to 30 mole percent of the total glycol components. The composition according to claim 2, wherein the bifunctional carboxylic acid is used as the main component of terephthalic acid or dimethyl terephthalate. The difunctional carboxylic acid according to claim 2 or 5, wherein the difunctional carboxylic acid is dimethylisophthalate, isophthalic acid, succinic acid, adipic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalate, 2, 6-naphthalenedica At least one component selected from the group consisting of carboxylic acid, dimethyl 2, 6-naphthalate, and 1,4-cyclohexanedicarboxylic acid is used in an amount of up to 30 mole% of the total acid component. . The resin composition according to claim 1 or 2, wherein the flame retardant of component (B) is melamine cyanurate. The resin composition according to claim 1 or 2, wherein the flame retardant adjuvant of component (C) is used alone or in a mixed state of antimony trioxide (Sb ₂ O ₃ ) and zinc borate. The composition according to claim 1 or 2, wherein the reinforcing agent of component (D) is glass fiber in the form of spheres, mats, filaments, or long fibers. The composition according to claim 1 or 2, further comprising polytetrafluoroethylene, which is an antidripping agent.