KR101891338B1 - Polycyclohexylenedimethyleneterephtalate resin composition comprising non-halogen flame retardant and flame retardant aid - Google Patents

Abstract

[화학식 2]

[화학식 3]

상기에서, m은 1 이상의 정수이고, R1과 R2는 서로 같거나 다른 알킬, 알콕시, 아릴, 아릴록시기 및 에틸기이고, M은 알카리토류금속, 알카리금속, 아연, 알루미늄 또는 철이며, R₃와 R₄는 서로 같거나 다른 종류의 수소원자, 아미노기, 아릴기 또는 탄소수 1부터 3까지의 유기 알킬기이다.The present invention relates to a polycyclohexylenedimethylene terephthalate resin or a modified flame retardant thermoplastic resin composition containing the polycyclohexylenedimethylene terephthalate resin and a polycyclohexylenedimethylene terephthalate resin by using a high heat resistance non-halogen flame retardant and a flame retardant aid in an appropriate ratio Halogen flame retardant thermoplastic polycyclohexylene dimethylene terephthalate resin composition excellent in flame retardancy due to the flame-retarding action thereof, and excellent in high heat resistance and discoloration resistance.
The present invention relates to a polycyclohexylenedimethylene terephthalate resin composition comprising a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), a flame retardant represented by the formula (2) and a melamine- Can be provided.
[Chemical Formula 1]

(2)

(3)

Alkoxy, aryl, aryloxy group and ethyl group; M is an alkaline earth metal, an alkali metal, zinc, aluminum or iron; R ₃ and R ₄ are the same or different, R ₄ are the same or different kinds of hydrogen atoms, amino groups, aryl groups or organic alkyl groups having 1 to 3 carbon atoms.

Description

TECHNICAL FIELD The present invention relates to a polycyclohexylenedimethylene terephthalate resin composition containing a non-halogen flame retardant and a flame retardant auxiliary,

The present invention relates to a polycyclohexylenedimethylene terephthalate resin composition comprising a non-halogen flame retardant and a flame retardant auxiliary agent, wherein the polycyclohexylenedimethylene terephthalate resin is mixed with a high heat-resistant non-halogen flame retardant and a flame- Halogen flame retardant thermoplastic polycyclohexylene dimethylene terephthalate resin composition excellent in flame retardancy due to the flame-retarding action thereof, and excellent in high heat resistance and discoloration resistance.

With the recent demand for high heat resistance as a material, there is an increasing need for a super engineering plastic which simultaneously satisfies the heat resistance at a continuous use temperature of 270 占 폚 or more, the complicated shape of the electronic material, and the moldability suitable for the manufacture of automobile parts. In particular, high heat-resistant polymer materials are used as key components for next-generation high-tech industries such as displays, solar cells, flexible plastic materials for electronics, space industry materials, and other electronic / semiconductor industries. Polymer materials with high transparency, low hygroscopicity, and low shrinkage characteristics, along with high heat resistance of 330 ° C or higher, are required for use as flexible plastic materials for displays and solar cells, but they have not been developed yet.

 Conventional synthetic resins are widely used for building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys, etc. due to their excellent chemical and mechanical properties. However, most synthetic resins are combustible materials, and flame retardation is indispensable depending on the application. Examples of the flame retardant include halogen flame retardants, inorganic phosphorus flame retardants composed of polyphosphoric acid flame retardants such as red phosphorus and ammonium polyphosphate, organic phosphorus flame retardants typified by triaryl phosphate ester compounds, antimony oxides such as metal hydroxide and flame retardant additives, It is widely known to use the compounds alone or in combination.

For example, JP-A-8-176343 discloses a flame-retardant synthetic resin composition containing a polyphosphoric acid ammonium, a polyhydric hydroxyl group-containing compound, a triazine ring-containing compound and a metal hydroxide with respect to a resin. In addition, US Patent Nos. 3936416 and 4010137 disclose flame retardant synthetic resin compositions containing melamine polyphosphate and erythritol (penta-tripenta) relative to the resin. Japanese Patent Application Laid-Open No. 11-152402 discloses a flame retardant synthetic resin composition containing polybutylene terephthalate (PBT), melamine pyrophosphate, and aromatic phosphate oligomer. In addition, U.S. Patent No. 4278591 and U.S. Patent No. 5618865 disclose that melamine pyrophosphate and other phosphorus compounds are effective for the destruction of polymers such as PBT. Further, JP-A-10-183124 discloses a flame retardant obtained from melamine, anhydrous phosphoric acid, and piperazine hydrate. However, these flame retardant effects are still insufficient, and a flame retardant that gives excellent flame retardancy with a small blending amount has been desired.

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. Polycyclohexylenedimethylene terephthalate (PCT) resin has a higher crystallization speed than PBT, but is much faster than PET and can be injection molded, but has high heat resistance and relatively high price competitiveness. Also, it is known that PCT has the highest melting point among existing polyester polymers (excluding liquid crystal polymer), and has low water absorption rate and excellent heat discoloration resistance of PA polymer.

In general, thermoplastic resins such as polycyclohexylene dimethylene terephthalate resin have been applied to many products due to their excellent processability and mechanical properties. However, since the thermoplastic resin itself is not resistant to fire, it is regulated by law in the world to use only the polymer which satisfies the flame retarding standard. Conventionally, as a technique for imparting flame retardancy to a resin, a formulation in which a halogen-based flame retardant and antimony oxide are mixed with a thermoplastic resin has been widely used. Organic halogen flame retardants and halogen-containing organophosphorus flame retardants are widely used because they have excellent flame retardant effects. However, when a halogen flame retardant is used, halogen compounds are volatilized during processing to generate hydrogen halide gas, The demand for non-halogen flame retardants and resins containing flame retardant additives has been rapidly expanding in recent years due to the problem of human harmfulness of gases generated during combustion.

Examples of the flame retardant and flame retardant auxiliary include inorganic flame retardants such as halogen-based flame retardants and polyphosphoric acid-based flame retardants such as ammonium polyphosphate, organophosphorus flame retardants typified by triaryl phosphate ester compounds, antimony oxides such as metal hydroxides or flame retardant stabilizers, Etc. have been used singly or in combination.

Of these, organic halogen flame retardants and halogen-containing organic phosphorus flame retardants have been widely used because of their excellent flame retardant effect. However, when a halogen flame retardant is used, halogen compounds are volatilized during processing to generate hydrogen halide gas, And the demand for a resin containing a non-halogen flame retardant agent is rapidly expanding due to the problem of human harmfulness of the gas generated in the combustion.

On the other hand, a polymer resin flame retarding technique using an inorganic compound such as magnesium hydroxide or aluminum hydroxide as a flame retardant using a non-halogen compound has been proposed. Japanese Patent Application Laid-Open No. 10-204,276 proposes a method of imparting flame retardancy to a resin by adding aluminum hydroxide (ATH) and at least one nitrogen compound and an agent to an unsaturated polyester resin. However, since a large amount of aluminum hydroxide must be used, the mechanical properties of the resin composition deteriorate. In addition, Korean Patent Publication No. 2007-0064924 discloses a flame-retardant technology for acrylonitrile-butadiene-styrene copolymer resin (ABS resin), which is a bromine-based organic compound.

1. Japanese Patent Application Laid-Open No. 8-176343 2. US Patent No. 3936416 3. US Patent No. 4010137 4. Japanese Patent Application Laid-Open No. 11-152402 5. US Patent No. 4278591 6. U.S. Patent No. 5618865 7. Japanese Patent Application Laid-Open No. 10-183124 8. Japanese Patent Application Laid-Open No. 10-204276 9. Korean Patent Publication No. 2007-0064924

The present invention relates to a flame retardant polycyclohexylenedimethylene terephthalate resin composition excellent in flame retardancy and excellent in heat resistance and discoloration resistance, which comprises a polycyclohexylenedimethylene terephthalate resin, a non-halogen phosphorus flame retardant, and a melanin- .

The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to one aspect of the present invention comprises a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), a flame retardant represented by the formula (2) And a melamine-based flame retarding auxiliary agent.

[Chemical Formula 1]

(2)

(3)

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 from each other, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, M is an alkaline earth metal, R ₃ and R ₄ are the same or different from each other, a hydrogen atom, an amino group, an aryl group or an organic alkyl group having 1 to 3 carbon atoms.

The flame retardant may be contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin having the repeating unit represented by the formula (1).

R ₁ and R ₂ in the above formula (2) may be the _{same or different} and are each a methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, ≪ / RTI >

The melamine-based flame retarding additive may be melamine cyanurate represented by the following formula (4) or melamine polyphosphate represented by the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above, n is an integer of 3 or more.

The melamine-based flame retarding additive may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin composed of the repeating unit represented by the formula (1).

The flame retardant polycyclohexylenedimethylene terephthalate resin composition may further comprise glass fiber. The glass fiber may be prepared by mixing 100 parts by weight of a polycyclohexylenedimethylene terephthalate resin having the repeating unit represented by the formula (1) 1 to 60 parts by weight based on 100 parts by weight of the composition.

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

In addition, a molded article having a flame retardancy of V-1 or more at a thickness of 1/8 "according to the UL 94 VB flame retarding specification can be provided.

The polycyclohexylenedimethylene terephthalate resin composition containing the non-halogen flame retardant and the flame retardant auxiliary according to the present invention is excellent in flame retardancy, heat resistance and discoloration resistance and does not contain a halogen compound causing environmental pollution during combustion It is environmentally friendly.

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.

The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to one aspect of the present invention comprises a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), a flame retardant represented by the formula (2) And a melamine-based flame retarding auxiliary agent.

[Chemical Formula 1]

(2)

(3)

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 from each other, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, M is an alkaline earth metal, R ₃ and R ₄ are the same or different from each other, a hydrogen atom, an amino group, an aryl group or an organic alkyl group having 1 to 3 carbon atoms.

Hereinafter, constituent components of the polycyclohexylenedimethylene terephthalate resin composition including the flame retardant non-halogen flame retardant and the flame retardant auxiliary 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 the repeating units of the above formula (1).

Polycyclohexylene dimethylene terephthalate resin has a higher crystallization speed than PBT but is much faster than PET and can be injection molded, has high heat resistance and relatively high price competitiveness, has a high potential for potential use, It is a polymer having the highest melting point among polyester-based polymers, and has a low water absorption rate compared to a PA-based polymer and is excellent in heat discoloration resistance.

In addition, the flame retardant polycyclohexylenedimethylene terephthalate resin according to an embodiment of the present invention includes the flame retardant represented by the general formulas (2) and (3). The compound represented by the above formula (2) is a phosphinic acid metal salt, which serves as a flame retardant and is used for preventing a decrease in tensile strength.

Preferably, R ₁ and R ₂ in Formula 2 are methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, A phenoxy group, and the like.

The M in Formula 2 may be selected from the group consisting of alkaline earth metals, alkali metals, zinc, aluminum, and iron. The flame retardant may be selected from the group consisting of primary ammonium phosphate, secondary ammoniumphosphate, ammonium phosphate, amine / amidephosphate, aminesulfate, melaminephosphate, A non-halogen flame retardant containing at least one selected from the group consisting of dimelaminephosphate, melaminepyrophosphate, melaminepolyphosphate, tricrecyl phosphate and trichloro alkylphosphate. And an inorganic compound such as magnesium hydroxide, aluminum hydroxide and the like.

The flame retardant may be contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin having the repeating unit represented by the formula (1). This is because when the flame retardant is contained in an amount of less than 0.1 part by weight with respect to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, the flame retardancy is deteriorated, and when it exceeds 50 parts by weight, the mechanical strength is lowered.

In addition, the flame retardant polycyclohexylene dimethylene terephthalate resin according to an embodiment of the present invention includes a melamine-based flame retardant auxiliary. Such a melamine-based flame retarding aid may be melamine derivatives, for example, melamine cyanurate represented by the following formula (4) or melamine polyphosphate represented by the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above, n is an integer of 3 or more.

In the above, melamine cyanurate or melamine polyphosphate acts as a complement to the phosphine metal salt used as a flame retardant, thereby enhancing flame retardancy and preventing degradation of tensile strength.

The melamine-based flame retarding additive may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin composed of the repeating unit represented by the formula (1). If the content is less than 0.1 parts by weight, the flame retardancy enhancing effect is insufficient. If the content is more than 50 parts by weight, the impact strength of the molded article is lowered.

In addition, according to one embodiment of the present invention, the flame retardant polycyclohexylene dimethylene terephthalate resin may further include glass fiber. The glass fibers may have a cross-sectional diameter of 10 to 100 mu m and a length of 1 to 20 mm.

The glass fiber may be contained in an amount of 1 to 60 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin having the repeating unit represented by the formula (1).

The flame retardant polycyclohexylenedimethylene terephthalate resin composition according to the present invention can be produced by compounding a polycyclohexylenedimethylene terephthalate resin, a flame retardant represented by the formula (2) and a flame retardant represented by the formula (3), and a melamine- .

According to another aspect of the present invention, there can be provided a molded article made from the polycyclohexylene dimethylene terephthalate resin composition, wherein the molded article has a flame retardancy according to the UL 94 VB flame retardancy of 1/8 & May be greater than or equal to -1

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

The SK Chemicals, Inc. poly-cyclohexylene dimethylene terephthalate resin (trade name PURATAN ^® was used.

(B) Nonhalogen Flame retardant Organic phosphinate

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

(C) Flame-retardant auxiliary

( C1 ) Melamine Cyanurate

Melamine cyanurate (trade name: Nonfla MC600) from Do boon Inc. was used.

( C2 ) Melamine Polyphosphate

A melamine polyphosphate compound (trade name MPP) was used.

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

1 to 60% by weight of GF (glass fiber) was compounded with respect to 100% by weight of the polycyclohexylenedimethylene terephthalate resin.

(E) Polybutylene terephthalate  Suzy

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

Example  1 to 4

(A) polycyclohexylenedimethylene terephthalate resin, (B) a non-halogen flame retardant, and (C) a flame retardant additive were blended at a composition ratio of the following Table 1 using HAAKE PolyDrive R600 of Thermo Electron Corporation at 280 to 300 ^° C To prepare a specimen.

Example  5 to 8

(B) a non-halogen flame retardant, and (C) a flame retardant additive were prepared by using the HAAKE PolyDrive R600 manufactured by Thermo Electron Corporation under the composition ratio shown in Table 2 below, using the above (D) polycyclohexylenedimethylene terephthalate -GF Specimens were prepared by compounding at temperatures ranging from 280 to 300 ^° C.

Comparative Example  One

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

Comparative Example  2

(E) 85 wt% of polybutylene terephthalate (PBT) resin, 8 wt% of non-halogen flame retardant (B), 7 wt% of melamine cyanurate (C1) The composition was prepared by compounding in a temperature range of 220 to 250 ^° C using HAAKE PolyDrive R600 from Thermo Electron Corporation.

Comparative Example  3

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

Comparative Example
(weight%) Example
(weight%) One 2 One 2 3 4 (A) 100 - 85 86 87 84 (B) - 8 6 7 8 8 (C) C1 - 7 9 7 - - C2 - - - - 5 8 (E) - 85 - - - - UL-94 Flammability (1/8 ") V-2 V-2 V-1 V-0 V-1 V-0

　

Comparative Example
(weight%) Example
(weight%) 3 5 6 7 8 (D) 100 85 86 86 88 (B) - 6 9 7 7 (C) (C1) - 9 5 - - (C2) - - - 7 5 UL-94 Flammability (1/8 ") No
class V-1 V-0 V-0 V-1

Test Example

Each of the specimens using the resin composition having the compositions 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 retardancy specification. The flame retardancy measured was shown in Tables 1 and 2 .

As with the flame retardance measurement results, the flame retardant polycyclohexylenedimethylene terephthalate resin composition according to the present invention is excellent in flame retardancy and is environmentally friendly since it does not contain a halogen compound causing environmental pollution during 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 (9)

1. A polycyclohexylenedimethylene terephthalate resin composition comprising a polycyclohexylenedimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), a flame retardant represented by the following formula (2), and a melamine-
Wherein the flame retardant is contained in an amount of 6 to 9% by weight based on the total weight of the polycyclohexylenedimethylene terephthalate resin composition.
[Chemical Formula 1]

(2)

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 from each other, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, M is an alkaline earth metal, Metal, zinc, aluminum, or iron. delete 2. The compound of claim 1, wherein R ₁ and R ₂ in Formula 2 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, , And a phenoxy group. The polycyclohexylene dimethylene terephthalate resin composition according to claim 1, The polycyclohexylenedimethylene terephthalate resin composition according to claim 1, wherein the melamine flame retarding auxiliary is melamine cyanurate represented by the following formula (4) or melamine polyphosphate represented by the following formula (5).
[Chemical Formula 4]

[Chemical Formula 5]

In the above, n is an integer of 3 or more. The melamine-based flame retardant additive according to claim 1, wherein the melamine-based flame retarding additive comprises 0.1 to 50 parts by weight of polycyclohexylenedimethylene terephthalate resin composed of the repeating unit represented by the formula (1) Phthalate resin composition. The polycyclohexylene dimethylene terephthalate resin composition according to claim 1, further comprising glass fiber. The polycyclohexylenedimethylene terephthalate resin composition according to claim 6, wherein the glass fiber is contained 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 units of the formula (1) Composition. 8. A molded article produced from the polycyclohexylenedimethylene terephthalate resin composition according to any one of claims 1 to 7. The molded article according to claim 8, wherein the flame retardancy according to UL 94 VB flame retardancy is V-1 or more at a thickness of 1/8 ".