KR101735883B1 - Polycarbonate resin composition and molded article using the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molded article produced from the polycarbonate resin composition, wherein the polycarbonate resin composition comprises (a) a polycarbonate resin; (b) needle-shaped reinforcement; (C) 0.01 to 2 parts by weight of the antimony ion exchanger (c) relative to 100 parts by weight of the sum of the polycarbonate resin (a) and the acicular stiffener (b) .
The polycarbonate resin composition of the present invention is excellent in heat resistance and heat resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition and a molded article produced therefrom,

The present invention relates to a polycarbonate resin composition and a molded article produced from the polycarbonate resin composition, and more particularly, to a polycarbonate resin composition excellent in thermal decomposition resistance capable of exhibiting excellent physical properties by preventing thermal decomposition of polycarbonate and a molded article produced therefrom will be.

Polycarbonate is one of engineering plastics and widely used in the plastics industry.

The polycarbonate has a glass transition temperature (Tg) of about 150 DEG C due to a bulk molecular structure such as bisphenol-A, exhibits a high heat resistance, and the carbonyl group of the carbonate group has high flexibility and flexibility . It is also an amorphous polymer and has excellent transparency.

In addition, it has excellent impact resistance and compatibility with other resins, and is used in a wide range of fields such as electric and electronic fields, optical devices, automobiles, architectural fields, medical fields, food containers and other living materials.

However, since the polycarbonate has a disadvantage that the fluidity is poor, the polycarbonate needs to be subjected to high-temperature molding, so thermal decomposition by heat can easily occur during polycarbonate molding, and a low molecular weight polycarbonate is produced as thermal decomposition proceeds, A problem arises. In general, such thermal decomposition can be further accelerated by the addition of inorganic fillers for the purpose of impact reinforcement.

Therefore, it is necessary to effectively prevent polycarbonate from undergoing thermal decomposition in a high-temperature environment so as to realize excellent physical properties.

To solve this problem, conventionally, an organic acid and / or silane-based coupling agent such as maleic acid or acetic acid is mixed with a polycarbonate to form a resin composition. Addition of an organic acid or a silane-based coupling agent has an effect of inhibiting thermal decomposition of the polycarbonate, but it causes a problem that physical properties such as mechanical strength are deteriorated. In particular, organic acids cause degradation of polymers in a high temperature processing process, which may degrade the properties and have a low boiling point, which can generate gas during processing.

Accordingly, in order to solve the above problems, the present invention has been carried out to produce polycarbonate having excellent thermal decomposition resistance while maintaining excellent properties inherent to polycarbonate.

Korean Patent Publication No. 10-2010-0017479 Korean Patent Laid-Open Publication No. 10-1999-0077921

It is therefore an object of the present invention to provide a polycarbonate resin composition having excellent mechanical strength by adding an inorganic filler capable of realizing high rigidity and a molded article produced therefrom.

Also, there is provided a polycarbonate resin composition capable of realizing excellent physical properties by reducing the thermal decomposition of polycarbonate by adding an ion exchanger capable of preventing thermal decomposition of polycarbonate accelerated by an inorganic filler, and a molded article produced therefrom .

According to an aspect of the present invention, there is provided a polycarbonate resin composition comprising: (a) a polycarbonate resin; (b) needle-shaped reinforcement; (C) 0.01 to 2 parts by weight of the antimony ion exchanger (c) relative to 100 parts by weight of the sum of the polycarbonate resin (a) and the acicular stiffener (b) .

The polycarbonate resin (a) and the acicular stiffener (b) may be composed of 60 to 95% by weight of the polycarbonate resin (a) and 5 to 40% by weight of the acicular stiffener (b).

The acicular stiffener (b) may be potassium titanate whisker.

The potassium titanate whiskers may have a length of 10 to 20 mu m and a diameter of 0.3 to 0.6 mu m.

The potassium titanate whisker may have a pH of 8 to 11.

The antimony ion exchanger (c) may include antimonic acid.

The antimony ion exchanger (c) may have an average particle diameter of 0.01 to 3 탆.

The molded article according to one embodiment of the present invention can be produced from the polycarbonate resin composition described above.

The molded article may have a melt index of 23 to 40 g / 10 min as measured according to ASTM D1238.

The molded article may have a flexural strength of 500 to 1,400 kgf / cm ^{2 as} measured according to ASTM D790.

The polycarbonate resin composition of the present invention is excellent in mechanical strength by adding an acicular stiffener and has excellent appearance characteristics as compared with conventional inorganic fillers due to the fine size of the acicular stiffener and is used for processing a molded article requiring dimensional stability There are advantages.

Also, it is possible to provide a polycarbonate resin composition in which an antimony-based ion exchanger is added to prevent thermal decomposition of polycarbonate generated by the action of the needle-like stiffener, thereby realizing excellent physical properties and a molded article produced therefrom.

The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the description of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, the polycarbonate resin composition of the present invention will be described.

The polycarbonate resin composition according to the present invention comprises a polycarbonate resin, an acicular stiffener and an antimony ion exchanger.

Each component of the polycarbonate resin composition according to one embodiment of the present invention will be described in detail.

(a) Polycarbonate resin

The polycarbonate resin (a) is a polyester having a carbonate bond, and the kind thereof is not particularly limited, and any polycarbonate usable in the resin composition field can be used.

As an example, the polycarbonate resin may be prepared by reacting a diphenol with phosgene, a halogen acid ester, a carbonic ester, or a combination thereof.

Two or more kinds of diphenols may be combined to constitute a repeating unit of a polycarbonate resin.

Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Among these diphenols, preferred are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- Hydroxyphenyl) cyclohexane can be used. Preferably, 2,2-bis (4-hydroxyphenyl) propane can be used.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.

The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like.

A specific example of the linear polycarbonate resin may be a bisphenol-A polycarbonate resin. Specific examples of the branched polycarbonate resin may be a polymer prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The resin with the polyester carbonate copolymer may be prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. The carbonate used herein may be a diaryl carbonate such as diphenyl carbonate or ethylene carbonate.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, and preferably 14,000 to 40,000 g / mol.

The polycarbonate resin may be 60 to 95% by weight, preferably 75 to 90% by weight, based on 100% by weight of the acicular reinforcing material (b) to be described later. When the polycarbonate resin is less than 60% by weight, the appearance characteristics are poor, and when it exceeds 95% by weight, the mechanical strength may be lowered.

(b) Needle-type reinforcement

The acicular stiffener (b) serves to improve the mechanical strength of the polycarbonate resin composition. As the acicular stiffener (b), potassium titanate whiskers can be used, and the potassium titanate whiskers can be fibrous potassium titanate.

Conventionally, a glass fiber is mainly used as an acicular reinforcing material. However, the polycarbonate resin composition to which the glass fiber is added may increase the mechanical strength, but the appearance of the glass fiber is deteriorated due to the protrusion of the glass fiber There is a limitation of the injection molding.

On the other hand, the potassium titanate whiskers have inherent high stiffness, abrasion resistance, and chemical resistance, and because of the fine size of whiskers, they can overcome the limitations of complicated structure and formability of existing fillers such as glass fiber, By using them in combination, it is possible to simultaneously improve mechanical strength and appearance characteristics.

The potassium titanate whisker can be specifically potassium hexatitanate (K ₂ Ti ₆ O ₁₃ ) whisker. The potassium hexatitanate is a potassium titanate having resistance to heat and chemical resistance, It can be advantageous for the processing of

The potassium titanate whiskers may have a length of 10 to 20 mu m and a diameter of 0.3 to 0.6 mu m. When the length and diameter of the potassium titanate whisker have the above range, excellent appearance characteristics can be realized.

In addition, the potassium titanate whisker may have a pH of 8 to 11, and preferably a pH of 9 to 10.

The acicular stiffener may be 5 to 40% by weight, preferably 10 to 25% by weight, based on 100% by weight of the polycarbonate resin. If the needle-like stiffener is less than 5% by weight, the mechanical strength may be lowered. If it exceeds 40% by weight, the appearance and workability may be deteriorated.

(c) antimony ion exchanger

The antimony ion exchanger (c) is an anion exchanger capable of capturing cations and has a role of suppressing the thermal decomposition of the polycarbonate resin.

The antimony-based ion exchanger is obtained by capturing potassium ions (K ⁺ ) of the needle-like stiffener, in particular, potassium titanate whiskers, to thereby thermally decompose the polycarbonate resin generated by the activity of titanium (Ti) in the potassium titanate whisker .

The antimony ion exchanger may have an average particle diameter of 0.01 to 3 탆, preferably 0.1 to 2 탆. Here, the average particle diameter means a cumulative weighted average value D50 measured using a particle size distribution measuring apparatus or the like by laser light diffractometry or the like.

The antimony ion exchanger may include antimony oxide and may specifically include antimony trioxide (Sb ₂ O ₃ ), antimony tetraoxide (Sb ₂ O ₄ ), or antimony pentoxide (Sb ₂ O ₅ ). Preferably, it may be in the form of a hydrate of antimony trioxide, antimony tetraoxide or antimony pentoxide, and more preferably antimonic acid in the form of hydrate of antimony pentoxide (Sb ₂ O ₅ .xH ₂ O).

The antimony ion exchanger may be 0.01 to 2 parts by weight, more preferably 0.25 to 1 part by weight based on 100 parts by weight of the sum of the polycarbonate resin and the acicular reinforcing material. When the amount of the antimony ion exchanger is less than 0.01 parts by weight, the thermal decomposition of the polycarbonate can not be effectively inhibited. When the amount is more than 2 parts by weight, the effect of improving the thermal decomposition effect is insignificant and uneconomical.

The polycarbonate resin composition may further include additives optionally according to the use thereof. The additive may further include a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer or a colorant, and may be used in a mixture of two or more kinds depending on the properties of the final molded product.

 The flame retardant is a material that reduces combustibility and may be a phosphate compound, a phosphite compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate compound or a melamine compound But it is not limited thereto.

The lubricant is a material that lubricates the surface of the metal in contact with the polycarbonate resin composition during processing, molding, or extrusion to aid flow or movement of the resin composition, and a commonly used material may be used.

The plasticizer is a material that increases the flexibility, workability, or extensibility of the polycarbonate resin composition, and a commonly used material can be used.

The heat stabilizer is a substance that inhibits thermal decomposition of the polycarbonate resin composition when kneaded or molded at a high temperature, and a commonly used material can be used.

The antioxidant is a substance which inhibits or prevents the chemical reaction of the polycarbonate resin composition with oxygen so that the resin composition is decomposed to lose its inherent physical properties. The antioxidant is a phenol type, phosphite type, thioether type or amine type antioxidant But it is not limited thereto.

The light stabilizer is a substance that inhibits or blocks the color change or loss of mechanical properties of the polycarbonate resin composition from ultraviolet rays, preferably titanium oxide.

Conventional pigments or dyes may be used as the colorant.

The additive may be contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the sum of the polycarbonate resin and the needle-shaped reinforcement.

The above-mentioned polycarbonate resin composition uses an acicular-type stiffener that is effective for improving mechanical strength as an inorganic filler and uses an antimony-based ion exchanger that can effectively control the thermal decomposition of the polycarbonate resin generated by the acicular stiffener Mechanical strength, appearance, and heat resistance.

The polycarbonate resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the polycarbonate resin composition according to the present invention may be prepared in the form of pellets by mixing the constituents of the present invention and other additives simultaneously, followed by melt extrusion in an extruder.

The molded article according to one embodiment of the present invention can be produced from the polycarbonate resin composition described above.

The polycarbonate resin composition is produced from a polycarbonate having a high molecular weight capable of exhibiting excellent physical properties by preventing thermal decomposition of the polycarbonate resin, and is excellent in thermal decomposition resistance and mechanical strength.

Specifically, the molded article may have a melt index of 23 to 40 g / 10 min, preferably 25 to 36 g / 10 min.

The bending strength of the molded article may be 500 to 1,400 kgf / cm ² , and preferably 600 to 1200 kgf / cm ² .

The polycarbonate resin composition is excellent in heat resistance and mechanical strength and can be applied to molded articles requiring such properties without limitation.

[Experimental Example]

Hereinafter, the results of experiments conducted to demonstrate the excellent effects of the polycarbonate resin composition of the present invention are shown.

The components used in the polycarbonate resin compositions of the following Examples and Comparative Examples are as follows.

(a) Polycarbonate resin

A polycarbonate resin product having a flow index of 29 g / 10 min and a weight average molecular weight of 22,000 g / mol was used at 250 ° C and 1.2 kg in accordance with ISO 1133 of Cheil Industries.

(b) Needle-type reinforcement

TISMO-D, a potassium titanate whisker product from Otsuka, was used.

(c) an ion exchanger

(c-1) IXE-300, an antimony ion exchanger product containing Sb ₂ O ₅ .4H ₂ O from Toagosei, was used.

(c-2) IXEPLAS-A1, an ion exchanger product mainly composed of zirconium (Zr), magnesium (Mg) and aluminum (Al) of Toagosei was used.

(c-3) IXEPLAS-A3, an ion-exchanger product whose surface is coated with an organic coating, is mainly made of Toagosei Zirconium (Zr), Magnesium (Mg) and Al (Al)

(Sigma-Aldrich) maleic acid was used instead of the (c-4) ion exchanger.

(acetic acid) manufactured by Sigma-Aldrich was used instead of the (c-5) ion exchanger.

The polycarbonate resin compositions of Examples and Comparative Examples were prepared in accordance with the ingredient content ratios described in Table 1 below. (A) and the needle-like stiffener (b) in Table 1 and the amount of the ion-exchanged material (c) based on 100 parts by weight of the sum of the polycarbonate resin (a) Parts by weight.

The components listed in Table 1 were dry mixed and melted and kneaded and compressed in a quantitative continuous feeding to a feeder of a twin-screw extruder (L / D = 25, 45 mm). Then, the polycarbonate resin composition pelletized through an extruder was dried at about 80 ° C for about 6 hours and then injected at about 280 ° C using an injection machine to prepare a specimen.

Constituent a b c-1 c-2 c-3 c-4 c-5 Example One 90 10 0.12 - - - - 2 90 10 0.25 - - - - 3 90 10 0.50 - - - - 4 90 10 1.00 - - - - 5 80 20 0.12 - - - - 6 80 20 0.25 - - - - 7 80 20 0.50 - - - - 8 80 20 1.00 - - - - 9 90 10 1.50 - - - - 10 90 10 2.00 - - - - Comparative Example One 90 10 - - - - - 2 80 20 - - - - - 3 80 20 - 0.50 - - - 4 80 20 - 1.50 - - - 5 80 20 - - 0.50 - - 6 80 20 - - 1.50 - - 7 90 10 0.005 - - - - 8 90 10 2.10 - - - - 9 90 10 - - - 1.50 - 10 90 10 - - - - 1.50

The flexural strength, melt index and weight average molecular weight of the polycarbonate resin compositions of Examples 1 to 10 and Comparative Examples 1 to 10 were evaluated. The evaluation method of each evaluation item is as follows, and the evaluation result is shown in Table 2 below.

≪ Evaluation of Flexural Strength >

Flexural strengths were measured for each of the specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 10 under the condition of 2.8 mm / min according to ASTM D790.

≪ Evaluation of melt flow index >

The flow index was measured at 250 DEG C and 1.2 kg according to ASTM D1238 for each of the specimens prepared by Examples 1 to 10 and Comparative Examples 1 to 10.

≪ Evaluation of weight-average molecular weight (Mw) >

Each of the pelletized polycarbonate resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 10 was subjected to gel permeation chromatography on the basis of standard polystyrene to obtain a weight average molecular weight -1 And the weight average molecular weight-2 of the specimen prepared by injection molding the pelletized polycarbonate resin composition was measured in the same manner.

Flexural strength
(kgf / cm ² ) Melt Index
(g / 10 min) Weight average molecular weight -1
(g / mol) Weight average molecular weight -2
(g / mol) Example One 770 30.6 18,800 17,000 2 1,140 24.4 22,800 20,500 3 798 23.9 20,900 19,000 4 620 32.3 19,200 17,300 5 803 34.3 18,200 16,400 6 1,001 28.6 19,400 17,500 7 1,199 25.5 23,300 21,000 8 834 31.1 19,300 17,400 9 602 35.1 18,600 16,800 10 590 35.9 17,800 16,200 Comparative Example One 380 40.7 15,800 13,400 2 414 58.1 14,500 12,300 3 356 45.6 13,300 11,300 4 373 43.8 13,200 11,200 5 324 51.8 12,700 10,800 6 257 58.3 12,500 10,600 7 380 39.0 16,000 13,800 8 482 37.8 15,500 14,000 9 350 39.1 15,800 14,400 10 370 38.5 16,000 15,400

From Table 1 and Table 2, it can be seen that the polycarbonate resin compositions according to Examples 1 to 10 are excellent in both mechanical strength and thermal decomposition resistance.

The polycarbonate resin compositions according to Examples 1 to 10 had large bending strength, small melt index, and large weight average molecular weight. This indicates that the thermal decomposition of the polycarbonate resin is inhibited by the addition of the antimony-based ion exchanger and the physical properties of the polycarbonate resin composition are improved.

On the other hand, the polycarbonate resin compositions to which the ion exchangers of Comparative Examples 1 and 2 were not added had lower mechanical strengths and smaller weight average molecular weights.

The polycarbonate resin compositions of Comparative Examples 3 to 6 also had smaller bending strengths and smaller weight average molecular weights and were smaller in weight average molecular weight than Comparative Examples 1 and 2 which did not use an ion exchanger.

The polycarbonate resin compositions of Comparative Examples 7 and 8 used the same ion exchangers as those of the examples but their contents were out of the range of the present invention. As a result, flexural strength and weight average molecular weight were smaller than those of the examples, It can be seen that the content of the ion exchanger is a major factor in the formation.

The polycarbonate resin compositions of Comparative Examples 9 and 10 used organic acids instead of ion exchangers, and found that the mechanical strength and the weight average molecular weight were small. It can be expected that the organic acid decomposes the polycarbonate resin.

In the case of Comparative Examples 1 to 10, the reason why the melt index was largely measured as compared with the Examples is that the fluidity is increased due to thermal decomposition of the polycarbonate resin in view of the fact that the weight average molecular weight is observed to be low.

The polycarbonate resin composition is required to have a certain level of fluidity in order to facilitate processing. However, when a low molecular weight polycarbonate resin is produced by thermal decomposition to increase fluidity, the resultant polycarbonate resin composition may deteriorate the physical properties of the resin composition have.

It was found that the thermal decomposition of the polycarbonate resin by the potassium titanate whisker can be effectively controlled when the antimony ion exchanger is used.

The scope of the present invention is not limited to the above-described embodiments, but may be embodied in various forms of embodiments within the scope of the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

(a) a polycarbonate resin;
(b) needle-shaped reinforcement; And
(c) an antimony ion exchanger,
0.01 to 2 parts by weight of the antimony ion exchanger (c) relative to 100 parts by weight of the sum of the polycarbonate resin (a) and the acicular stiffener (b)
Wherein the needle-like stiffener (b) is a potassium titanate whisker having a pH of 8 to 11.
The method according to claim 1,
The polycarbonate resin (a) and the needle-like stiffener (b)
60 to 95% by weight of the polycarbonate resin (a) and
And 5 to 40% by weight of the acicular stiffener (b).
delete The method according to claim 1,
Wherein the potassium titanate whisker has a length of 10 to 20 占 퐉 and a diameter of 0.3 to 0.6 占 퐉.
delete The method according to claim 1,
The antimony ion exchanger (c) comprises an antimonic acid.
The method according to claim 1,
Wherein the antimony ion exchanger (c) has an average particle diameter of 0.01 to 3 탆.
A molded article produced from the polycarbonate resin composition according to any one of claims 1, 2, 4, and 6 to 7.
9. The method of claim 8,
The molded article has a melt index of 23 to 40 g / 10 min as measured according to ASTM D1238.
9. The method of claim 8,
Wherein the molded article has a flexural strength of 500 to 1,400 kgf / cm ^{2 as} measured according to ASTM D790.