KR20140034063A - Non-halogen flame-retarding polycyclohexylenedimethyleneterephtalate resin composition - Google Patents

Abstract

The present invention relates to a polycyclohexylenedimethylene terephthalate resin composition having excellent flame retardant properties, and excellent heat resistance and discoloration resistance. The polycyclohexylenedimethylene terephthalate resin composition, according to one embodiment of the presenet invention, comprises: a polycyclohexylenedimethylene terephthalate resin comprising a repeating unit represented by the chemical formula 1; and a flame retardant agent represented by the chemical formula 2, wherein the content of the flame retardant agent represented by chemical formula 2 is 8 to 13 wt%. ′Chemical formula 1′ ′Chemical formula 2′ wherein m is an integer greater than or equal to 1, n is an integer of 1 - 4 inclusive, R1 and R2 are identical or different alkyl groups, alkoxy groups, aryl groups or aryloxy groups, and M is an alkaline-earth metal, an alkali metal, zinc, aluminum, or iron.

Description

Non-halogen flame-retardant polycyclohexylenedimethyleneterephtalate resin composition

The present invention relates to a non-halogen flame-retardant polycyclohexylenedimethylene terephthalate resin composition, and more particularly to a non-halogen flame-retardant polycyclohexylenedimethylene terephthalate resin composition excellent in flame retardancy and excellent in heat resistance and discoloration resistance. It is about.

Recently, as the demand for high heat resistance of materials increases, the necessity of a super engineering plastic that satisfies both heat resistance of continuous use temperature of 270 ° C. or higher and moldability suitable for manufacturing complex-shaped electronic materials and automobile parts is increasing. In particular, high heat-resistant polymer materials are used as core component materials for next-generation high-tech industries such as displays, solar cells, flexible plastic materials for electronic paper, space industry materials, and other electronic / semiconductors. In order to be used as a flexible plastic material for displays and solar cells, a polymer material having high transparency, low hygroscopicity and low shrinkage property with high heat resistance of 330 ° C. or higher is required but has not been developed yet.

In order to ensure the heat resistance of the polymer, it is necessary to have a very stable molecular structure in the heat through introduction of aromatic. However, low transparency due to interaction between aromatic polymer chains, optical anisotropy, and high thermal expansion coefficient of the organic polymer itself are obstacles to development.

Recently, new super engineering plastics are being developed to replace PEEK (Poly (Ether Ether Ketone)) which satisfies heat resistance but is poor in formability. Typical polymers include i) PA-based PA46 (Stanyl®, DSM), PPA (Polyphthalamide or PA6T or Nylon6T; typical products include Zytel HTN, Amodel and Grivory) and PA9T (or Nylon9T; Genestar®, ii) Ester-based liquid crystalline polymer (LCP; hereinafter LCP; typical products such as Xydar and Sumikasuper), and iii) polyester-based PCT (Poly (Cyclohexylene dimethylene terephthalate)) derived from aliphatic ring compound monomer; representative product Thermx of DuPont. There is.

Among them, PCT has a slower crystallization rate than PBT, but is much faster than PET and can be injection molded, but has high heat resistance and relatively high price competitiveness. In addition, this PCT is the polymer having the highest melting point among the existing polyester polymers, except for the liquid crystal polymer, and is known to have a low water absorption rate and excellent heat discoloration resistance compared to the PA polymer.

In general, thermoplastic resins such as polycyclohexylenedimethylene terephthalate resins have been applied to many products due to their excellent processability and mechanical properties. On the other hand, since the thermoplastic resin itself is not resistant to fire, it is regulated by the law to use only polymer resin satisfying the flame retardant standard in the world. Conventionally, a method of mixing a halogen-based flame retardant and antimony oxide into a thermoplastic resin has been used as a technique for imparting flame retardancy to a resin. However, since halogen-based flame retardants have a fatal effect on the human body and the environment, the flame retardant technology using environmentally friendly non-halogen compounds is required.

On the other hand, a polymer resin flame retardant technique using inorganic compounds such as magnesium hydroxide and aluminum hydroxide has been proposed as a flame retardant using a non-halogen compound. Japanese Patent Application Laid-open No. Hei 10-204276 discloses a method of imparting flame retardancy to a resin by adding aluminum hydroxide (ATH), at least one nitrogen compound, and a red to a unsaturated polyester resin. However, since a large amount of aluminum hydroxide must be used, there is a disadvantage in that the mechanical properties of the resin composition are lowered. In addition, Korean Patent Publication No. 2007-0064924 discloses a flame retardant technology of acrylonitrile-butadiene-styrene copolymer resin (ABS resin), but there is a problem that the flame retardant used is a bromine-based organic compound, which is not environmentally friendly.

1. Japanese Patent Application Laid-Open No. 10-204276 2. Korean Patent Publication No. 2007-0064924

The present invention is a polycyclohexylenedimethylene terephthalate resin and a non-halogen flame-retardant polymer having the highest melting point among polyester polymers except liquid crystal polymer, and having low water absorption rate and excellent heat resistance and discoloration resistance as compared with PA polymers. It is to provide a flame-retardant polycyclohexylenedimethylene terephthalate resin composition that is environmentally friendly and excellent flame retardant containing a phosphorus-based flame retardant having excellent flame retardant performance compared to the existing inorganic compound, and excellent in heat resistance and discoloration resistance.

Flame retardant polycyclohexylenedimethylene terephthalate resin composition according to an aspect of the present invention, comprising a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit of the formula (1), and a flame retardant represented by the formula (2) , The content of the flame retardant represented by Formula 2 is 8 to 13% by weight.

[Formula 1]

(2)

Wherein m is an integer of 1 or more, n is an integer of 1 to 4, R ₁ and R ₂ are the same or different alkyl groups, alkoxy groups, aryl groups, or aryloxy groups, and M is an alkaline earth metal, an alkali Metal, zinc, aluminum, or iron.

In addition, R ₁ and R ₂ in Formula 2 are methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy group, and phenoxy group. It may be selected from the group consisting of.

In addition, the flame-retardant polycyclohexylenedimethylene terephthalate resin composition may further comprise a glass fiber, the glass fiber to 100 parts by weight of a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit of Formula 1 It may be included in an amount of 1 to 60 parts by weight.

According to another aspect of the present invention, a molded article made of the polycyclohexylenedimethylene terephthalate resin composition may be provided.

In addition, molded articles having a flame retardancy of at least V-1 at a thickness of 1/8 "in accordance with the UL 94 VB flame retardant specification may be provided.

According to another aspect of the present invention, an engineering plastic made of the polycyclohexylenedimethylene terephthalate resin composition may be provided.

The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to the present invention is excellent in flame retardancy, heat resistance and discoloration resistance, and is environmentally friendly because it does not contain a halogen compound that causes environmental pollution during combustion.

The present invention is capable of various modifications and various embodiments, and specific embodiments are described in detail in the description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Flame retardant polycyclohexylenedimethylene terephthalate resin composition according to an aspect of the present invention, comprising a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit of the formula (1), and a flame retardant represented by the formula (2) , The content of the flame retardant represented by Formula 2 is 8 to 13% by weight.

[Formula 1]

(2)

　　

Wherein m is an integer of 1 or more, n is an integer of 1 to 4, R ₁ and R ₂ are the same or different alkyl groups, alkoxy groups, aryl groups, or aryloxy groups, and M is an alkaline earth metal, an alkali Metal, zinc, aluminum, or iron.

Hereinafter, the components of the flame retardant polycyclohexylenedimethylene terephthalate resin composition of the present invention will be described in detail.

The flame retardant polycyclohexylenedimethylene terephthalate resin according to an embodiment of the present invention includes a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit of Chemical Formula 1.

Polycyclohexylenedimethylene terephthalate resin is slower than PBT but crystallization rate is much faster than PET, and it is possible to injection molding, but it has high heat resistance and relatively high price competitiveness. It is the polymer having the highest melting point among polyester-based polymers, has a lower water absorption than PA-based polymers, and is very excellent in heat discoloration resistance.

In addition, the flame-retardant polycyclohexylenedimethylene terephthalate resin according to an embodiment of the present invention includes a flame retardant represented by the formula (2).

 The compound represented by the formula (2) is a phosphinic acid metal salt, serves as a flame retardant, and is used to prevent a decrease in tensile strength.

Preferably, R ₁ and R ₂ of Formula 2 are methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy group, and It may be selected from the group consisting of phenoxy group.

M of Formula 2 may be selected from the group consisting of alkaline earth metals, alkali metals, zinc, aluminum, and iron. The flame retardant is primary ammonium phosphate (Primaryammoniumphospate), secondary ammonium phosphate (Secondary ammoniumphospate), ammonium phosphite (Ammoniumphospite), amine / amide phosphate (Amine / Amidephophate), aminesulfate (melamine phosphate) Melamine phosphate (Dimelaminephosphate), Melaminepyrophosphate (Melaminepyrophosphate), Melaminepolyphosphate (Melaminepolyphosphate), Tricrecyl phosphate (Tricrecyl phosphate), and trichloroalkyl phosphate (Trichloro alkyl phosphate) containing at least one selected from It can be selected from the group consisting of organic compounds which are flame retardants, and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.

And, the flame retardant may be included in 8 to 13% by weight of the total resin composition. It is a problem that the flame retardancy is lowered when the flame retardant is included in less than 8% by weight, the tensile strength is lowered to 20MPa or less when included in excess of 13% by weight, it is difficult to apply to engineering plastics such as automotive parts materials Because of this.

In addition, according to an embodiment of the present invention, the flame retardant polycyclohexylenedimethylene terephthalate resin may further include glass fiber. The diameter of the glass fiber cross section may be 10-100 μm, and the length may be 1-20 mm.

The glass fiber may be included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin composed of the repeating unit of Formula 1.

The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to the present invention may be prepared by compounding a polycyclohexylenedimethylene terephthalate resin and a flame retardant represented by Chemical Formula 2 as described above.

According to another aspect of the present invention, a molded article made of the polycyclohexylenedimethylene terephthalate resin composition may be provided, and the molded article may have a V of a flame retardancy of 1/8 "according to UL 94 VB flame retardant specification. May be greater than or equal to -1.

According to another aspect of the present invention, an engineering plastic made of the polycyclohexylenedimethylene terephthalate resin composition may be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

The components of the polycyclohexylenedimethylene terephthalate resin composition were prepared as follows.

(A) Polycyclohexylenedimethylene terephthalate  Suzy

Polycyclohexylenedimethylene terephthalate resin (trade name: Puratan®) of SK Chemicals was used.

(B) Nonhalogen Flame retardant Organic phosphinate

Organic phosphinate (trade name: Exolit OP 1240) manufactured by Clariant was used.

(C) Polycyclohexylenedimethylene terephthalate - GF ( Glass fiber ) Composite resin

1 to 60% by weight of GF (Glass fiber) based on 100% by weight of the polycyclohexylenedimethylene terephthalate resin was compounded.

(D) Polybutylene terephthalate  Suzy

Polybutylene terephthalate resin (trade name VB-5150G) manufactured by Cheil Industries was used.

Example  One

90% by weight of the (A) polycyclohexylenedimethylene terephthalate resin and 10% by weight of (B) non-halogen flame retardant were compounded using a HAAKE PolyDrive R600 from Thermo Electron Corporation at a temperature range of 280 to 300 ° C. Prepared.

Example  2 to 4

The (A) polycyclohexylenedimethylene terephthalate resin and (B) non-halogen flame retardant were compounded at a temperature range of 280 to 300 ° C. using HAAKE PolyDrive R600 of Thermo Electron Corporation at a composition ratio shown in Table 1. Prepared.

Example  5

90% by weight of the (C) polycyclohexylenedimethylene terephthalate-GF (Glass fiber) composite resin and 10% by weight of (B) non-halogen flame retardant using a HAAKE PolyDrive R600 of Thermo Electron Corporation at a temperature of 280 to 300 ℃ Specimens were prepared by compounding in the range.

Example  6 to 8

The (C) polycyclohexylenedimethylene terephthalate-GF (Glass fiber) composite resin and (B) non-halogen flame retardant using a HAAKE PolyDrive R600 of Thermo Electron Corporation at a composition ratio shown in Table 2 at a temperature of 280 to 300 ℃ Specimens were prepared by compounding in the range.

Comparative Example  One

100% by weight of the polycyclohexylenedimethylene terephthalate resin (A) was compounded using a HAAKE PolyDrive R600 manufactured by Thermo Electron Corporation at a temperature range of 280 to 300 ° C to prepare a specimen.

Comparative Example  2

90% by weight of the (D) polybutylene terephthalate (PBT) resin and 10% by weight of the (B) non-halogen flame retardant are compounded in a temperature range of 220 to 250 ° C. using a HAAKE PolyDrive R600 of Thermo Electron Corporation. Was prepared.

Comparative Example  3

95% by weight of the (A) polycyclohexylenedimethylene terephthalate resin and 5% by weight of the (B) non-halogen flame retardant were compounded using a HAAKE PolyDrive R600 from Thermo Electron Corporation at a temperature range of 280 to 300 ° C. Prepared.

Comparative Example  4

93% by weight of the (A) polycyclohexylenedimethylene terephthalate resin and 7% by weight of the (B) non-halogen flame retardant were compounded using a HAAKE PolyDrive R600 from Thermo Electron Corporation at a temperature range of 280 to 300 ° C. Prepared.

Comparative Example  5

86% by weight of the (A) polycyclohexylenedimethylene terephthalate resin and 14% by weight of the (B) non-halogen flame retardant were compounded using a HAAKE PolyDrive R600 from Thermo Electron Corporation at a temperature range of 280 to 300 ° C. Prepared.

Comparative Example  6

100% by weight of the (C) polycyclohexylenedimethylene terephthalate-glass fiber (GF) composite resin was compounded using a HAAKE PolyDrive R600 manufactured by Thermo Electron Corporation at a temperature range of 280 to 300 ° C. to prepare a specimen.

Comparative example (% by weight) Example (% by weight) One 2 3 4 5 One 2 3 4 (A) 100 - 95 93 86 90 92 89 87 (B) - 10 5 7 14 10 8 11 13 (D) - 90 - - - - - - - UL-94 Flammability (1/8 ") V-2 V-2 V-2 V-2 V-0 V-0 V-0 V-0 V-0 Tensile Strength (MPa)
40 32 28 26 18 23 25 21 20

Comparative example (% by weight) Example
(weight%) 6 5 6 7 8 (C) 100 90 89 88 87 (B) 10 11 12 13 UL-94 Flammability (1/8 ") No
class V-1 V-1 V-1 V-0 Tensile Strength (MPa) 122 81 73 63 52

Test Example

Each of the specimens using the resin composition having the composition shown in the above Examples and Comparative Examples was measured for flame retardancy at a thickness of 1/8 "according to UL 94 VB flame retardant regulations, and the tensile strength of each specimen was measured. , And tensile strengths are shown in Tables 1 and 2 above.

As shown in the flame retardancy and tensile strength measurement results, it can be seen that the flame retardancy is reduced in Comparative Examples 3 and 4 having a flame retardant content of less than 8% by weight, the tensile strength of Comparative Example 5 having a flame retardant content of more than 13% by weight It can be seen that the lowering. The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to the present invention was excellent in flame retardancy, and did not contain a halogen compound that causes environmental pollution at the time of combustion.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (7)

To include a polycyclohexylene dimethylene terephthalate resin composed of a repeating unit of the formula (1), and a flame retardant represented by the formula (2),
A flame retardant polycyclohexylenedimethylene terephthalate resin composition having a content of the flame retardant represented by Chemical Formula 2 is 8 to 13% by weight.
[Chemical Formula 1]

(2)

Wherein m is an integer of 1 or more, n is an integer of 1 to 4, R ₁ and R ₂ are the same or different alkyl groups, alkoxy groups, aryl groups, or aryloxy groups, and M is an alkaline earth metal, an alkali Metal, zinc, aluminum, or iron. According to claim 1, R ₁ and R ₂ in the formula 2 is methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy group And flame retardant polycyclohexylenedimethylene terephthalate resin composition selected from the group consisting of phenoxy groups. The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to claim 1, further comprising glass fibers. The flame-retardant polycyclohexylenedimethylene terephthalate resin according to claim 3, wherein the glass fiber is included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin composed of the repeating unit of Chemical Formula 1. Composition. A molded article made of the polycyclohexylenedimethylene terephthalate resin composition according to any one of claims 1 to 4. The molded article according to claim 5, wherein the flame retardancy according to the UL 94 VB flame retardant specification is V-1 or more at a thickness of 1/8 ". An engineering plastic made from the polycyclohexylenedimethylene terephthalate resin composition according to any one of claims 1 to 4.