KR20160069133A - Halogen free transparent flame retardant polycarbonate resin composition and molded product - Google Patents

Abstract

The present invention relates to a highly transparent halogen-free polycarbonate flame retardant resin composition and a molded article. According to the present invention, the use of a specific halogen-free metal salt flame retardant prevents bubble formation in a high temperature injection molding process even if the thickness of the injected product exceeds 5 mm. Therefore, it is possible to provide the molded article exhibiting satisfactory transparency and flame retardancy in the level of UL94V V-0 required for injection of lighting products.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a halogen-free polycarbonate flame retardant resin composition having high transparency and a molded article thereof. BACKGROUND ART < RTI ID = 0.0 &

The present invention relates to a halogen-free, highly transparent polycarbonate flame retardant resin composition and a molded article, and more particularly, to a polycarbonate flame retardant resin composition and a molded article thereof having a halogen-free metal flame retardant having a high injection molding temperature When the thickness of the product is thick, the shrinkage occurs due to the temperature difference between the inside and outside of the conventional product, and also the problem that the metal salt component of the flame retardant decomposes the polycarbonate resin and thus bubbles are generated, Carbonate flame retardant resin composition and a molded article produced from the composition.

Polycarbonate resin is a generic name of a polymer compound having a carbonic ester-type structure in which an impact strength and a tensile strength are balanced. The polycarbonate resin is excellent in mechanical properties and hardly changes in strength due to temperature change. Therefore, it is used in machinery, electric parts, It has transparency close to glass, and is used in the field of illumination. A flame retardant may be added to impart flame retardancy.

In order to impart various properties thereto, the additive added thereto lowers the transparency and the physical properties thereof are different from the conventional ones. In particular, a flame retardant is added in order to impart flame retardancy, and a flame retardant capable of obtaining flame retardancy while maintaining transparency is limited. In addition, a metal flame retardant (KPBS: Potassium perfluoro butyl sulfonate) is generally used as a flame retardant capable of obtaining a flame retardancy with only a small amount, without significantly impairing the basic physical properties of the polycarbonate.

However, these metal flame retardants also affect the transparency performance depending on the addition amount. The addition amount is about 0.1%, and the transparency is lowered as the addition amount is increased, and the lower the addition amount, the lower the flame retardancy. Thus, there are various products having an appropriate level of flame retardant, and all of them are promoted to a polycarbonate resin having both transparency and flame retardancy.

However, as the use of the product is diversified, it is used in various types of products. In certain cases, transparency deteriorates. A large amount of air bubbles are generated in the thick part of the product during injection molding and the appearance becomes hazy (haze occurrence).

That is, since the metal salt component affects the decomposition of the polycarbonate resin, in the case of the product using the flame retardant, there is no abnormality in the transparency at the thin part in the injection molding, but when the thickness of the product is thick (about 5 mm or more) In the case of the polycarbonate resin in which the injection molding is carried out at a considerably high temperature as compared with the resin of the flame retardant, the shrinkage occurs due to the temperature difference between the inside and the outside of the product, and the metal salt component of the flame retardant decomposes the polycarbonate resin, There is a problem in that it can not be used in an illumination field product where transparency is impaired and transparency is required.

When the polycarbonate flame retardant resin composition has a large thickness under high temperature injection molding temperature, shrinkage occurs due to the temperature difference between the inside and outside of the conventional product, and as the metal salt component of the flame retardant decomposes the polycarbonate resin, It is urgently required to develop an environmentally friendly polycarbonate flame retardant resin composition capable of eliminating the problems that have occurred and giving high transparency.

In order to solve the problems of the prior art as described above, the present invention relates to a polycarbonate flame retardant resin composition having high transparency for use in a molded article of an illumination field, using a halogen-free metal salt flame retardant, V-0 together to provide a molded article having high transparency.

In order to achieve the above object,

There is provided a transparent polycarbonate flame retardant resin composition comprising a polycarbonate resin and an aromatic sulfonesulfonate-aromatic sulfone disulfonate-based metal salt flame retardant.

Further, the present invention provides a molded article molded from the above-mentioned transparent polycarbonate flame retardant resin composition.

According to the present invention, there is provided an effect of providing a polycarbonate flame retardant resin composition having flame retardancy (V-0 rating) and high transparency required for use in molded articles without bubbles in a thick part of the article and a molded article produced from the composition have.

Fig. 1 is a photograph of a specimen (127 mm x 13 mm x 6.4 mm) of a sample manufactured according to Example 1 of the present invention, and it can be confirmed that bubbles are not generated.
FIGS. 2 and 3 are photographs of specimens (127 mm.times.13 mm.times.6.4 mm) prepared according to Comparative Examples 1 and 2 of the present invention, respectively.
FIG. 4 is a photograph (127 mm.times.13 mm.times.6.4 mm) of the sample of the sample prepared according to Comparative Example 3 of the present invention, and it can be confirmed that less than 5 bubbles were generated.

Hereinafter, the present invention will be described in detail.

The transparent polycarbonate flame retardant resin composition of the present invention is characterized by including a polycarbonate resin and an aromatic sulfonesulfonate-aromatic sulfonesulfonate disulfide-based metal salt flame retardant.

The above-mentioned "aromatic sulfonesulfonate-aromatic sulfones disulfonate-based metal salt flame retardant" refers to a non-halogenated metal salt flame retardant unless otherwise specified.

The transparent polycarbonate flame retardant resin composition of the present invention is a halogen-free flame retardant resin composition wherein, unless otherwise specified, the term "halogen-free" means that the flame retardant of a non- Even when the halogen content is taken into account, it means that the halogen content in the resulting resin composition is 1000 ppm or less in total.

As a specific example, the transparent polycarbonate flame retardant resin composition comprises 100 parts by weight of a polycarbonate resin and 100 parts by weight of an aromatic sulfonesulfonate-aromatic sulfonesulfonate-based metal salt flame retardant More than 0.01 To 0.2 By weight.

As another example, the transparent polycarbonate flame retardant resin composition may include 100 parts by weight of a polycarbonate resin, 100 parts by weight of an aromatic sulfonesulfonate-aromatic sulfonesulfonate-based metal salt flame retardant More than 0.01 to 0.15 , And phosphate-based antioxidant 0.01 to 1 part by weight.

As another example, the polycarbonate flame retardant resin composition having high transparency may include 100 parts by weight of a polycarbonate resin, 100 parts by weight of an aromatic sulfonesulfonate-aromatic sulfonesulfonate-based metal salt flame retardant From 0.01 to 0.15 parts by weight, from 0.01 to 1 part by weight of a phosphate antioxidant, and from 0.1 to 2 parts by weight of at least one lubricant selected from pentaerythritol tetrastearate and polyethylene wax .

As another example, the polycarbonate flame retardant resin composition having high transparency may include 100 parts by weight of a polycarbonate resin, 100 parts by weight of an aromatic sulfonesulfonate-aromatic sulfonesulfonate-based metal salt flame retardant From 0.01 to 0.15 parts by weight, from 0.01 to 1 part by weight of a phosphate antioxidant, from 0.1 to 2 parts by weight of at least one lubricant selected from pentaerythritol tetrastearate and polyethylene wax, and And 0.1 to 2 parts by weight of a benzotriazole-based UV stabilizer.

The aromatic sulfonesulfonate-aromatic sulfone disulfonate-based metal salt flame retardant may be, for example, a mixed metal salt of a complex of diphenylsulfonesulfonate and diphenylsulfonesulfonate.

The aromatic sulfonesulfonate-aromatic sulfone disulfonate-based metal salt flame retardant may be, for example, a non-halogenated compound represented by the following formula 1, and HES2-FR of ARICHEM may be used as a commercially available product.

[Formula 1]

M ₁ M ₂ SO ₃ -R ₁ -R ₄ -SO ₂ -R ₄ -SO ₃ (wherein R ₁ and R ₄ are independently selected aromatic hydrocarbon groups,

M ₁ and M ₂ are independently selected from Li, Na, K, Fe, Al, Ca, Zn, Ba and Mg)

R ₁ and R ₄ may independently be a phenyl or diphenyl group.

M ₁ and M ₂ may independently be Li or K.

The metal salt flame retardant may be used in an amount of more than 0.01 to 0.2 parts by weight, or 0.02 to 100 parts by weight based on 100 parts by weight of the polycarbonate resin. To 0.15 parts by weight. In this range, the flame retardancy measured by the UL 94 method is maintained at V-0, and even when the thickness of the article to be injection molded at a high temperature is as thick as 5 mm or more, It has an effect of providing transparency.

For reference, in the case of a metal flame retardant of halogen-based sulfonate as a conventional metal flame retardant, for example, potassium perfluoro butane sulfonate, if the thickness of the product is thicker than 5 mm, bubbles and haze It is possible to show a drastic decrease in the physical properties in terms of transparency.

Examples of the phosphate antioxidant include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,4- . ≪ / RTI >

The phosphate-based antioxidant may be used in combination with a hindered phenol-based antioxidant. The hindered amine compound may be, for example, a halogen-free alkoxyhindered amine having Mw of 2200 to 2300 g / mol,

[Formula 2]

이다)로 표시되는 주쇄를 갖는 트리아진 화합물일 수 있다.
(Wherein R is

Is a triazine compound having a main chain represented by the following formula

The phosphate-based antioxidant may be, for example, 0.01 to 1 part by weight or 0.03 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin, and the effect of preventing discoloration and mechanical property deterioration under the melt processing or high- .

Examples of the benzotriazole-based UV stabilizer include 2- (2'-Hydroxy-5'-t-octylphenyl) -benzotriazole, product name Cyasorb UV- 5'-methylphenyl) -5-chloro-benzotriazole, product name Tinuvin-326), 2- (2'-Hydroxy-3 ', 5'- (2'-hydroxy-3,5-di-tert.amylphenyl) benzotriazole, product name Tinuvin-328) 2'hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole (product name: Tinuvin-234) , Product name: Tinuvin-320), and 2- (2H-benzotrizol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol.

The UV stabilizer may be contained in an amount of 0.1 to 2 parts by weight, or 0.1 to 1% by weight, based on 100 parts by weight of the polycarbonate resin, and the ultraviolet absorbing effect can be maximized within this range.

As the UV stabilizer, a UV stabilizer based on HALS may also be used.

The polycarbonate resin has a melt index (MI) of 0.1 to 30 g / 10 min (ASTM D1238, 300 DEG C, 1.2 kg load) or 2.5 to 30 g / 10 min (ASTM D1238, Load). ≪ / RTI >

The polycarbonate flame retardant resin composition having high transparency may contain at least one selected from a lubricant, an antioxidant, a chain extender, a catalyst, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, And may further include additives. However, antifogging agents may be excluded as additives. The additive can be used, for example, within a range that does not adversely affect the physical properties of the polycarbonate flame retardant resin composition having high transparency of the present invention.

For reference, the polycarbonate flame retardant resin composition having high transparency has a V-0 rating of flame retardancy measured under the UL94 (2.0 mm) standard under a non-anti-drip agent, and haze (3 mm chip) %.

The polycarbonate flame retardant resin composition having high transparency is a specimen having a thickness of 5 mm or more, and does not hinder transparency because bubbles are not generated during injection molding.

According to the present invention, even when the polycarbonate flame retardant resin composition having a high transparency is used and the thickness of the article is thicker than 5 mm, no bubbles are generated under high-temperature injection molding, and the UL94V V A flame retardancy of -0, and a molded article conforming to the transparency quality can be provided. The polycarbonate flame retardant resin composition having high transparency of the present invention can be subjected to ordinary extrusion molding, injection molding, and the like.

For reference, the injection molding temperature may be in the range of 200 to 300 占 폚, the extrusion temperature may be 220 占 폚 or higher, and the mold temperature may be in the range of 40 to 120 占 폚.

The illumination product may be, for example, a lens, a reflection sheet, an optical sheet, a reflector, an LED illumination, a light diffusion product, or the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[Example]

Example 1, Comparative Examples 1 to 3

The ingredients shown in the following Table 1 were put into a super mixer in the stated amounts and mixed well. The mixture was melt-kneaded in a temperature range of 200 to 300 占 폚 using a twin-screw extruder And then pellets were obtained. This pellet was injection-molded at 300 캜, and the mold temperature was 40 to 120 캜. The resulting specimen (127 mm x 13 mm x 6.4 mm) was used as a test specimen.

The flame retardance and haze were measured according to the UL94V standard, and the presence of bubbles was visually confirmed.

For reference, the materials used in the experiments are as follows:

≪ (PC) Polycarbonate resin >: The melt index (MI) of a polymer of bisphenol A was measured according to ASTM D1238 as the weight (g) measured at a temperature of 300 DEG C and a load of 1.2 kg for 10 minutes, A polycarbonate resin having a melt index of 14 g / 10 min, a PDI of 2.4 and an Mw of 45,000 g / mol was used.

<Flame Retardant-1>: As the non-halogen metal salt flame retardant, the product name HES2-FR (corresponding to Formula 1) of ARICHEM, which is an aromatic sulfonesulfonate-aromatic sulfonesulfonate type metal salt flame retardant, was used.

<Flame Retardant-2>: As the halogen metal salt flame retardant, RM65, a product of MITENI SpA, which is potassium perfluoro butane sulfonate (structural formula: CF ₃ -CF ₂ -CF ₂ -CF ₂ -SO ₃ K) was used.

<Flame Retardant-3>: As a halogen metal salt flame retardant, R-103, a product of HIROMASTER Co., Ltd., in which potassium perfluoro butane sulfonate (structural formula: CF ₃ -CF ₂ -CF ₂ -CF ₂ -SO ₃ K) was modified with lactone was used.

<Flame Retardant-4>: Halogen metal salt flame retardant: Hubei Hengxin Chemical Co., Ltd., having a composition of potassium perfluoro butane sulfonate (structural formula CF ₃ -CF ₂ -CF ₂ -CF ₂ -SO ₃ K, molecular weight 338.2, density 0.690, pH 5-7) HX98 & lt ; / RTI & gt ;

&Lt; Antioxidant &gt;: IRGAFOS 168 product name of BASF was used as a phosphate-based antioxidant.

& Lt; Lubricant &gt;: PETS was used as pentaerythritol tetrastearate.

<UV stabilizer> was used 2- (2'-hydroxy-3 ' , 5'-di (1,1-imethylbenzyl) phenyl] Product name Tinuvin 234 as -2H-benzotriazol.

[Test Example]

The properties of the specimens made from the polycarbonate flame retardant resin composition having high transparency prepared in Example 1 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

[Property measurement test]

* Flame retardancy : Measured at a thickness of 2.0 mm in a UL94 vertical method.

* Haze ( 3.0 mm chip): Measured with JIS J7136 as Hazemeter (HM-150) instrument.

* Bubbles: Bubbles were checked to see if the bubbles were visually inspected. Bubbles were observed under normal conditions. Bubbles were observed in five or more bubbles.

* Usage amount is based on 100 parts by weight of PC.

As shown in Table 1, in the case of the specimen made of the polycarbonate flame retardant resin composition having high transparency according to the present invention (Example 1), no bubbles were observed even when the thickness of the specimen was 6.4 mm thick Good level, see Figure 1), haze and flame retardancy also improved.

On the other hand, in Comparative Examples 1 to 3 in which flame retardants 1 to 3 were respectively replaced as comparable sulfonate-based metal salt flame retardants under the same conditions, a large amount of bubbles were produced (Comparative Example 1, defect level, see FIG. 2) (Comparative Example 2, normal level, see Fig. 4), and the air bubbles were also generated at a moderate level (Comparative Example 3, moderate level, see Fig. 4) It was confirmed that the bubble was generated when the thickness of the product was thick.

<Additional Experimental Example>

An experiment in which the content of flame retarder-1 in Example 1 was changed to 0.06 parts by weight (hereinafter referred to as Additional Example 1) and the content of Flame Retardant-1 in Example 1 were replaced with 0.15 part by weight (Hereinafter referred to as "Comparative Example 1") in which the content of flame retarder-1 in Example 1 was changed to 0.01 part by weight, and the content of flame retarder-1 was replaced by an improper excess of 0.4 part by weight The same experiment as in Example 1 was repeated except that one experiment (hereinafter, referred to as a further Comparative Example 2) was carried out.

As a result, in a further Example 1, the HAZE was 0.8, no bubbles were observed, the flame retardancy grade satisfied V-0, in a further Example 2 the HAZE was 2.8, no bubbles were observed, The grade satisfied the V-0 rating, while in the further Comparative Example 1, the HAZE was 0.4, no bubbles were observed, but the flame retardancy was in the V-2 grade, not the intended V- HAZE was at a level of 6.8 which inhibited the transparency, the flame retardancy was V-0, and no air bubbles were observed.

Therefore, in the present invention, the amount of the flame retarder-1 to be used is within the range of more than 0.01 to 0.2 parts by weight, preferably more than 0.01 to 0.15 parts by weight based on 100 parts by weight of the polycarbonate resin. When the thickness of the article is thicker than 5 mm, It was confirmed that the flame retardancy grade V0 was satisfied and the haze phenomenon was also prevented.

As a result, according to the present invention, an eco-friendly polycarbonate flame retardant resin having flame retardancy and high transparency of UL94V V-0 grade required for use in illumination products without causing air bubbles even when the thickness of the article is thicker than 5 mm Compositions can be provided.

Claims (16)

Polycarbonate resins and aromatic sulfonesulfonate-aromatic sulfones disulfonate-based metal salt flame retardants.
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
The aromatic sulfonesulfonate-aromatic sulfonesulfonate metal salt flame retardant is contained in an amount of more than 0.01 to 0.2 part by weight based on 100 parts by weight of the polycarbonate resin.
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
The resin composition contains a phosphate-based antioxidant, a lubricant, and Benzotriazole-based UV stabilizers. &Lt; RTI ID = 0.0 &gt;
Transparent polycarbonate flame retardant resin composition. The method of claim 3,
Wherein the phosphate-based antioxidant is in a range of 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate resin contained in the resin composition
Transparent polycarbonate flame retardant resin composition. 5. The method of claim 4,
The phosphate-based antioxidants include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,4- , And &lt; RTI ID = 0.0 &gt;
Transparent polycarbonate flame retardant resin composition. The method of claim 3,
Wherein the lubricant is in a range of 0.1 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin contained in the resin composition
Transparent polycarbonate flame retardant resin composition. The method according to claim 6,
Wherein the lubricant is at least one selected from pentaerythritol tetrastearate and polyethylene wax
Transparent polycarbonate flame retardant resin composition. The method of claim 3,
Wherein the benzotriazole-based UV stabilizer is in a range of 0.1 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin contained in the resin composition
Transparent polycarbonate flame retardant resin composition. 9. The method of claim 8,
The benzotriazole UV stabilizer is 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole, product name Cyasorb UV-541) 2- ), 2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole, product name Tinuvin- (2'-hydroxy-3,5-di-tert.amylphenyl) benzotriazole, product name Tinuvin-328) 3 ', 5'-di (t-butylphenyl) benzotriazole, product name Tinuvin-234) -320) and 2- (2H-benzotrizol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, product name Tinuvin-329)
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the aromatic sulfonesulfonate-aromatic sulfones disulfonate-based metal salt flame retardant is a mixed metal salt of a complex of diphenylsulfonesulfonate and diphenylsulfonesulfonesulfonate
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
The aromatic sulfonesulfonate-aromatic sulfone disulfonate-based metal salt flame retardant
Is a non-halogenated compound represented by the following formula
Transparent polycarbonate flame retardant resin composition
[Formula 1]
M ₁ M ₂ SO ₃ -R ₁ -R ₄ -SO ₂ -R ₄ -SO ₃
(Wherein R ₁ and R ₄ are independently selected aromatic hydrocarbon groups,
M ₁ and M ₂ are independently selected from Li, Na, K, Fe, Al, Ca, Zn, Ba and Mg) The method according to claim 1,
Wherein the polycarbonate resin has a melt index (MI) of 0.1 to 30 g / 10 min (ASTM D1238, 300 DEG C, 1.2 kg load)
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the transparent polycarbonate flame retardant resin composition comprises at least one additive selected from a lubricant, an antioxidant, a chain extender, a catalyst, a releasing agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a fuming inhibitor and a coupling agent &Lt; RTI ID = 0.0 &gt;
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
The transparent polycarbonate flame retardant resin composition is characterized in that the flame retardancy measured under the UL94 (2.0 mm) standard under a non-anti-drip agent has a V-0 rating and haze (3 mm chip) is 3.0 or less
Transparent polycarbonate flame retardant resin composition. The method according to claim 1,
Wherein the transparent polycarbonate flame retardant resin composition is applied to a specimen of a specimen having a thickness of 5 mm or more
Transparent polycarbonate flame retardant resin composition. An injection molded article for a lighting product comprising the transparent polycarbonate flame retardant resin composition of claim 1.

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