KR930003804B1 - Polycarbonate resin composition - Google Patents

Abstract

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Description

Polycarbonate resin composition

The present invention relates to a polycarbonate resin composition, and more specifically, to a polycarbonate resin composition having excellent releasability and good heat resistance and hydrolysis resistance.

Polycarbonate is widely used in various fields because of its excellent transparency, mechanical properties and dimensional stability.

In order to improve the antistatic properties of polycarbonates, antistatic polycarbonate compositions in which fatty acid monoglycerides are added to polycarbonates have been proposed (JP-A 55-4141 / 1930).

However, since this is not enough thermal stability, the thermostable polycarbonate composition which added the phosphorus compound, such as a phosphorous acid and a phosphite, is proposed (JP-A 51-44552 / 1976).

However, when the phosphorus compound is added in an amount of 0.001% by weight (10 ppm) or more, the hydrolysis resistance is very weak.

An object of the present invention is to solve the drawbacks of the prior art and to provide a polycarbonate resin composition that is excellent in heat resistance, hydrolysis resistance, and excellent in releasability.

That is, this invention is 0.05 weight part-1 weight part of (A) (beta) long-chain alcohol / benhenic acid ester or long chain aliphatic alcohol with respect to 100 weight part of polycarbonate resin, and (B) phosphorous acid and a phosphite ester It is to provide a polycarbonate resin composition comprising at least one phosphorus compound selected from the group consisting of 0-0.001 parts by weight in terms of personnel.

The polycarbonate resin which is the basis of the composition of the present invention is represented by the following general formula.

In the above formula, R ¹ , R ² , R ³ and R ⁴ represent a substituent such as a hydrogen atom, a hydrocarbon or a halogen atom.

Such a polycarbonate resin is a solvent method, i.e., reaction of a carbonate precursor such as dihydric phenol and phosgene or divalent phenol and diester carbonate in the presence of a well-known acid acceptor and a molecular weight regulator in a solvent such as methylene chloride. It can be prepared by transesterification with a carbonate precursor such as (diphenyl carbonate).

Bisphenols are suitably used as the dihydric phenol, and 4,4'-dihydroxyphenylpropane (bisphenol A) is particularly preferable. Moreover, you may use what substituted one part or all part of bisphenol A with another bivalent phenol.

As bivalent phenol other than bisphenol, it is a hydroquinone, 4, 4'- dihydroxy diphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4- Compounds such as hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide or bis (4-hydroxyphenyl) ether, and bis (3,5-dibromo And halogenated bisphenols such as 4-hydroxyphenyl) propane and bis (3,5-dichloro-4-hydroxyphenyl) propane.

These dihydric phenols may be homopolymers, interpolymers or mixtures thereof of dihydric phenols.

The polycarbonate resin used in the present invention may be a thermoplastic random bronched polycarbonate in which a polyfunctional aromatic compound is reacted with a dihydric phenol and / or a carbonate precursor.

From the point of mechanical strength and moldability, the polycarbonate resin used for this invention has a viscosity average molecular weight of 10,000-100,000, and especially 14,000-35,000.

In the present invention, as the component (A), β-long chain alcohol / behenic ester or long chain aliphatic alcohol is used.

Here, β-long side alcohol / behenic acid ester is a compound represented by the following general formula.

In the above formula, R ⁵ represents an alkyl group having 10 to 13 carbon atoms, R ⁶ represents an alkyl group having 10-11 carbon atoms, and R ⁷ represents a behenyl group (C ₂₂ H ₄₅ −).

Examples of such esters include 2-tetradecene dodecanebehenic acid ester, 2-octadecenedodecane behenic acid ester and 2-octadecene undecene behenic acid ester, and the like, among which 2-tetradecene dodecane. Kan behenic acid esters are preferred.

In addition, the long-chain aliphatic alcohol is represented by the general formula CnH _{2n + 1} OH, higher alcohols (n is 25 or more) is preferred, for example, hexacosanol-1, octacosanol-1, nacosanol, melisyl Alcohol etc. are used suitably.

Thus, the compounding quantity of (A) component is 0.05-1 weight part with respect to 100 weight part of polycarbonate resins, Preferably 0.07-0.8 weight part is good.

If the compounding quantity of (A) component is less than 0.05 weight part, a mold release pressure will become high and noise may generate | occur | produce at the time of mold release in some cases. On the other hand, if it exceeds 1 part by weight, these additives may bleed, causing the resin to become cloudy or degrade heat resistance.

In the present invention, at least one phosphorus compound selected from the group consisting of phosphorous acid and phosphorous acid ester is used as the component (B). Here, as the phosphite ester, one used as a general heat stabilizer or an antioxidant may be used, and either monophosphite or diphosphite may be used. Examples of the monophosphite include tris (2,4-di-t-butylphenyl) phosphite and tris (mono or di-nonylphenyl) phosphite.

As dephosphite,

In the formula, R ⁸ and R ⁹ may be the same as or different from each other, and a diphosphite represented by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms is used.

Specific examples include distearyl pentaerythritol diphosphite, dioctyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, Bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, dicyclo hexylpentaerythritol diphosphite and tetrakis (2,4-di-t-butylphenyl) -4, 4'-biphenylene phosphite etc. are mentioned.

Among these, aromatic phosphite esters such as trisnonylphenyl phosphite and trisphenyl phosphite are preferable.

The component (B) is used in an amount of 0-0.001 parts by weight, preferably 0-0.0008 parts by weight, in terms of the number of people, based on 100 parts by weight of the polycarbonate resin. When this compound (B) is added in an appropriate amount, heat resistance and hydrolysis resistance are improved. However, when 0.001 part (10 ppm) is added, hydrolysis resistance is significantly deteriorated. In this sense, it is better to use (B) component as little as possible.

In this invention, the usage-amount of (B) component can be reduced as much as possible using said (A) component. Moreover, in this invention, paraffin wax can be used as (C) component as needed. It is preferable to use a softening point of 75-90 ° C for this paraffin wax, and particularly preferably a softening point of 80-90 ° C. Moreover, it is preferable that this paraffin wax has an average carbon number of 37-40, especially 38-40.

Although such paraffin wax belongs to petroleum wax, the softening point differs from those of microcrystalline wax and petroleum. The paraffin wax is preferably in the form of a solid or powder. In this case, the diameter of the particles is preferably about 1 mm. Of course, it is also possible to warm, melt and mix and add the solid paraffin wax above the softening point.

If the softening point of this paraffin wax is less than 75 ° C, the heat resistance decreases and ΔYI rises in the evaluation of the heat resistance, which is not preferable. On the other hand, when it exceeds 90 degreeC, it is not good because a release pressure increases, compatibility with polycarbonate decreases, and transparency falls slightly.

Such paraffin wax may be used by mixing two or more kinds. When using this paraffin wax as (C) component, it is 0.05-1 weight part with respect to 100 weight part of said polycarbonate resin, Preferably it mix | blends in the ratio of 0.1-0.6 weight part. If the compounding ratio of (C) component is less than 0.05 weight part, mold release pressure may become high and noise may generate | occur | produce at the time of mold release.

On the other hand, if it exceeds 1 part by weight, the additive spreads, which is not good because it makes the resin cloudy. In addition, when using this (C) component, the compounding quantity of each of (A) component and (C) component is as above-mentioned, but the total amount of (A) component and (C) component is 0.1-1 weight part, Preferably Should be 0.3-0.8 parts by weight.

If the total amount of both is less than 0.1 part by weight, the release pressure is high, and noise is not good at the time of release. On the other hand, when the total amount of both exceeds 1 weight part, it will become turbid and it will not remarkably deteriorate commodity value.

As mentioned above, in this invention, various additives can be mix | blended if necessary in addition to said (A), (B) and (C) component added to polycarbonate resin as needed, unless the effect of this invention is reduced. have.

For example, glass fibers, carbon fibers, metal fibers, inorganic fillers, metal powders, ultraviolet absorbers, flame retardants, colorants and the like can be blended.

The polycarbonate resin composition of the present invention may be produced by blending the above components and mixing and kneading. The compounding and mixing method can be performed by conventional methods, for example, ribbon blender, Henschel mixer, Bambury's mixer, drum tumbler, single screw extruder, double screw It can carry out with an extruder, a cokneader, a multi-screw screw extruder, etc.

The heating temperature at the time of mixing kneading | mixing is suitable normally 250-300 degreeC.

As described above, the polycarbonate resin composition of the present invention is excellent in heat resistance, hydrolysis resistance, and good releasability. Therefore, the polycarbonate resin composition of the present invention, for example, by applying a variety of molding barriers such as injection molding, extrusion molding, compression molding, calendar molding, rotational molding, etc., structural parts, such as electrical and electronic equipment, office automation equipment and automobile parts, especially large This thin part is effective for injection molded products requiring products with good mold release properties.

The present invention will be described in more detail with reference to the following examples.

[Example 1-11 and Comparative Example 1-6]

(A), (B), and (C) component were mix | blended with the polycarbonate resin shown in the 1st table | surface, and this was premixed and kneaded with the drum tumbler, and then mixed and kneaded at 270 degreeC with the extruder, and the polycarbonate resin composition was obtained. This composition was tested by the method shown below. The results are shown in the first table.

[Test Method]

(1) Heat resistance (△ YI)

The cylinder temperature is 290 ℃, mold temperature 90 ℃, injection time 20 seconds, using a 15oz injection molding machine and a mold that can make 80mm × 80mm × 3mm (thick) molding pieces with a runner (diameter 6mm, length 80mm). Molding was continuously performed at a cooling time of 20 seconds, back pressure of 5 Kg / Cm ² G, and a screw speed of 46 rpm.

The yellow index (YI) is measured in accordance with JIS K-7103 for the molded article in the first shot and the sixty shot, and the difference (ΔYI) is shown. Small ΔYI indicates excellent heat resistance.

(2) Release property (Kg / Cm ² )

The pressure generated in the ejector was measured using a coaxial cyliner having a length of 35 mm, a diameter of 40-42 mm, and a wall thickness of 2 mm.

(3) metal rust

Check with eyes

(4) Long term heat resistance (△ YI)

The yellowness index test piece molded under the standard molding condition of (1) was left for 14 days in an oven at 140 ° C, and then the yellow index was measured. The difference (ΔYI) is shown.

(5) hydrolyzable

The yellowness measurement test piece molded under the standard molding condition of (1) above was exposed to 120 ° C saturated steam for 48 hours, and the change in appearance and the average molecular weight of the viscosity were measured. The decrease amount (ΔMv) of the molecular weight was shown.

[Table 1]

* 1 PC: Bisphenol A polycarbonate, Igemi Sekiyu Chemical Co., Ltd. "Taglon FN 2200" viscosity average molecular weight 22,100

* 2 β-long side alcohol / behenic acid ester, Nippon Yushi Co., Ltd. product.

* 3 Long-chain aliphatic alcohol: C ₂₆ H ₅₃ OH, manufactured by Nippon Yushi Co., Ltd., UNICEF UNA

* 4 Phosphorus compound: Trisnonylphenyl phosphite, Sumitomo Chemical Co., Ltd. product. Smeizer TNP

* 5 paraffin wax

○ paraffin wax , Nippon Seiro Co., Ltd. product "HNP-16" Average carbon number 39.5, softening point 89.0 degrees Celsius

○ paraffin wax , Nippon Seiro Co., Ltd. product "HNP-9", average carbon number 37.1, softening point 75.1 degrees Celsius

○ paraffin wax

Paraffin wax / Paraffin wax Blended product at 50/50, softening point 82 ° C

* 6 Glycerine monostearate: 0.3 parts by weight of a Lieju Vitamin Co., Ltd. product, "Liermal S-100A" was combined.

* 7 Mold friction occurs during mold release

Claims (10)

At least one member of the group consisting of 0.05-1 parts by weight of (A) β-long side alcohol / behenic acid ester or long chain aliphatic alcohol and (B) phosphorous acid and phosphorous acid ester is used based on 100 parts by weight of polycarbonate resin. A polycarbonate resin composition comprising 0-0.001 parts by weight of a phosphorus compound in the form of a phosphorus compound. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin has a viscosity average molecular weight in the range of 10,000-100,000. The polycarbonate resin composition according to claim 1, wherein the β-long chain alcohol / behenic acid ester is a compound represented by the following general formula. In the formula, R ⁵ represents an alkyl group having 10 to 13 carbon atoms, R ⁶ represents an alkyl group having 10-11 carbon atoms, and R ⁷ represents a behenyl group. The polycarbonate resin composition according to claim 1, wherein the long chain aliphatic alcohol is a compound represented by the general formula CnH _{2n + 1} OH, wherein n is 25 or more. The polycarbonate resin composition according to claim 1, wherein the amount of the component (A) is blended in an amount of 0.07 to 0.8 parts by weight based on 100 parts by weight of the polycarbonate resin. The polycarbonate resin composition according to claim 1, wherein the phosphite ester is trisnonylphenyl phosphite or trisphenyl phosphite. The polycarbonate resin composition according to claim 1, wherein the amount of (B) component is blended at 0-0.0008 parts by weight with respect to 100 parts by weight of polycarbonate resin. The polycarbonate resin composition according to claim 1, wherein the composition further mixes (C) paraffin wax in an amount of 0.05-1 part by weight based on 100 parts by weight of the polycarbonate resin. The polycarbonate resin composition according to claim 8, wherein the average carbon number of the paraffin wax is 37-40. The polycarbonate resin composition according to claim 8, wherein (C) component is blended at 0.1-0.6 part by weight based on 100 parts by weight of polycarbonate resin.