JPH03163161A - Stabilized aromatic polycarbonate composition and its preparation - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate composition lowly discolored in recycle molding and excelling in hot water resistance and thermal aging resistance by adding two specified phosphorous ester stabilizers to a chlorine-free aromatic polycarbonate. CONSTITUTION:A stabilized aromatic polycarbonate composition is obtained by adding 0.0005-0.015 pt.wt. at least one compound selected from a phosphorous diester [e.g. bis(nonylphenyl)hydrogen phosphite] and a phosphorous monoester (e.g. phenyl dihydrogenphosphite) and 0.0005-0.1 pt.wt. compound selected from among a phenolic antioxidant (e.g. Irganox(R) 1010), a phosphorous triester [e.g. tris(2,4-di-tert-butylphenyl) phosphite] and an organic phosphonite (e.g. tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate) to 100 pts.wt. substantially chlorine-free aromatic polycarbonate (e.g. a polycarbonate obtained by subjecting a crystalline aromatic polycarbonate to solid state polymerization).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a stabilized composition of aromatic polycarbonate, which is one of engineering plastics.

[Prior art]

Aromatic polycarbonate 1. is generally produced by a phosgene method or a melt method. This aromatic polycarbonate has the problem of coloring and molecular weight reduction during hot melt molding, and methods of adding various heat stabilizers to prevent this are known.

As the heat stabilizer, various compounds such as phosphorous triester, epoxy compound, and hindered phenol are used. Phosphite triesters include tris(nonylphenylphosphite, tris(
Examples include 2,4-di-t-butyl phosphite, and 4,4'-biphenylene diphosphinic acid tetrakis (2,4-di-t-butylphenyl) is also used. The amount added is usually 0.02 to 1 part by weight per 100 parts by weight of polycarbonate.

It is also known to add phosphorous acid diesters.

For example, Japanese Patent Publication No. 37-13775 reports a composition of aromatic polycarbonate and phosphorous diester, and the preferable amount of phosphorous diester added is 0.02 to 100 parts by weight of aromatic polycarbonate. It is said to be 5 parts by weight.

Further, JP-A-47-12993 reports a composition of aromatic polycarbonate and phosphorous acid diester. In this case, a chlorine atom-containing aromatic polycarbonate polymerized by the phosgene method is used, and the preferable amount of phosphite diester added thereto is 0.01 to 2.0 parts by weight per 100 parts by weight of the polycarbonate. It is in the range of 0 parts by weight.

However, although these phosphate ester-based heat stabilizers have a remarkable effect on short-term thermal stability during melt processing and molding, they do not improve the coloring and hot water resistance and steam resistance of molded objects during recycling molding. The problem is that it has a negative effect on the properties and coloring of the polymer during long-term heat aging. This bad influence depends on the amount added, and the larger the amount added, the worse the hot water resistance and polymer coloring described above have been.

On the other hand, in order to improve the hydrolysis resistance, JP-A-62-235
Publication No. 357 describes a method in which the amount of phosphorus compound added is determined according to the amount of chlorine atoms remaining in the polymerer, and the amount of remaining alkali metal or alkaline earth metal is determined according to the amount of phosphorus compound. has been done.

In the examples, 00 parts by weight of polycarbonate i obtained by the phosgene method contained 0.0037 to 0.00 chlorine atoms.
48 parts by weight remain, and to this, organic phosphine and phosphite triester are added as phosphorus compounds from 0.0040 to 0.
．． 012 parts by weight were added.

It is stated that in this method, hydrolysis resistance is improved. However, when we tried again with the same formulation, the improvement in heat resistance was not sufficient, and the degree of coloration was large when recycled molding was performed. Further, as a method for adding a phosphorus compound, there is mentioned Japanese Patent Application Laid-Open No. 58-89648.

This publication describes a composition in which polycarbonate is blended with an organic phosphite and an organometallic compound. It is stated that excellent thermal stability and hydrolysis resistance cannot be obtained by blending only an organic phosphite ester or an organometallic compound with polycarbonate.

In the example, polycarbonate 1 polymerized by the phosgene method
0.04 to 0.00 parts by weight of phosphite triester
0.05 parts by weight and 0.01 to 0.05 parts by weight of an organometallic compound.

As a comparative example, when an organic phosphite is used alone, a large amount of phosphite triester is present, 0.04 to 0.05 parts by weight relative to 100 parts by weight of polycarbonate polymerized by the phosgene method. has been added.

This method is said to have good molecular weight retention in heat resistance and hot water resistance tests, but when we retested the same formulation, we found that the pellets were colored during molding, and that the coloring was worse when recycled molding was performed. It was big.

As mentioned above, industrially produced polycarbonate produced by the phosgene method contains 0.005 parts by weight or more of chlorine per 100 parts by weight of polycarbonate (Japanese Patent Publication No. 59-22743). ). To this chlorine-containing polycarbonate, a number of stabilizers have been added. However, a stabilized composition that solves all of the problems of heat resistance, hot water resistance, and coloring during recycled molding has not been obtained. In addition, it has been reported that industrially produced aromatic polycarbonates manufactured by the melt method are colorless and transparent, and have somewhat poor physical strength (Kobunshi Vol. 27, p. 521, 1978). ).

Therefore, it can be said that it has been difficult to obtain colorless and transparent polycarbonate using the conventional melt method. Further, even when a stabilizer was added to the polycarbonate, the effect of improving heat resistance and hot water resistance was not sufficient.

Thus, until now, no polycarbonate has been known that satisfies all of the requirements of heat resistance, hot water resistance, and recyclability.

[Problem to be solved by the invention]

The present invention provides a novel aromatic polycarbonate composition that exhibits very little discoloration in recycled molds, has excellent hot water resistance, and has excellent heat aging resistance.

[Means to solve the problem]

The present inventors added a previously unthinkable trace amount of a compound with an IFi or higher selected from phosphorous diesters and phosphorous acid monoesters to an aromatic polycarbonate that does not substantially contain chlorine atoms, and further added phenol. By combining one or more compounds selected from antioxidants, phosphite triesters, and organic phosphonites,
The inventors have discovered that the above-mentioned problems can be achieved and have arrived at the present invention.

That is, the present invention provides an aromatic polycarbonate 1 containing substantially no chlorine atoms.
0.00 parts by weight, 0.0005 to 0.015 parts by weight of one or more compounds selected from phosphorous diesters and phosphorous monoesters (component a), phenolic antioxidant, phosphorous triester , and one or more compounds selected from organic phosphonites (b
component) 0.0005 to 0.1 part by weight, and a method for producing the same.

The present invention will be explained in detail below.

The aromatic polycarbonate referred to in the present invention has the formula; O It is expressed as

In the formula, Ar' represents a divalent aromatic residue. Further, p is an integer.

Such aromatic residues include, for example, phenylene (various types), naphthylene (various types), biphenylene (various types), pyridylene (various types), and the general formula; -A r2-Z-A
A divalent aromatic group represented by r3-- (II) can be mentioned.

Here, Ar2 and Ar3 are divalent aromatic groups which may be the same or different, such as phenylene (various), naphthylene (various), biphenylene (various), pyridylene (various), etc. represents the group of 2 is a simple bond or 101-co- -s- -so2-, ~
Represents a divalent group such as CO2-CON (R''')-.

(Here, RI R2 R3, R4 may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a cycloalkyl group, and l( is 3 to
Represents an integer of 11. ) Furthermore, such divalent aromatic groups (i.e., Arl,
or in Ar2, Ar3), one or more hydrogen atoms may be substituted with other substituents that do not adversely affect the reaction, such as a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a phenoxy group, a vinyl group, a cyano group, ester group,
It may be substituted with an amide group, a nitro group, or the like.

Such an aromatic group includes, for example, a substituted or unsubstituted phenylene group represented by: a substituted or unsubstituted biphenylene group represented by atoms, lower alkyl groups having 1 to 4 carbon atoms, lower alkoxy groups having 1 to 4 carbon atoms, cycloalkyl groups, or phenyl groups, which may be the same or different from each other, m and n is an integer from 1 to 4, and when m is 2 or more, R5 may be different, and n
is 2 or more, R6 may be different from each other).

Among these structures, Ar' is is preferred.

moreover, Those containing 85 mol% or more of repeating units are preferred.

X is -H or R7 I = climb It is.

Here, R7 is hydrogen, an alkyl group, an aralkyl group, an alkoxy group, etc., to name a few.

The polycarbonates include those having a branched structure containing a small amount of substituted or unsubstituted aromatic groups of trivalent or higher valence.

Furthermore, it is also possible to include an ester bond in the main chain structure within a range that does not impair the effects of the present invention.

The polycarbonate is substantially free of chlorine atoms, and specifically, 1) a method for measuring chlorine ions by potentiometric titration using an A-g NO s solution shows that chlorine ions are 0.00
0.005% by weight or less, and at the same time 11) In the method of measuring chlorine atoms by the combustion method, the chlorine atoms are o. oot
mm% or less.

Preferably 1) chloride ion is 0.0 below the detection limit of the above measurement method.
0001% by weight or less, and at the same time 11>chlorine atoms are
．． oot% by weight or less.

Any aromatic polycarbonate produced by any method can be used as long as it does not substantially contain chlorine atoms.

However, 1.0 g of the polycarbonate is mixed with methylene chloride 7
ml of the solution was placed in a cell of optical path controller 1 (7) and measured using a spectrophotometer. Absorbance at 400na+ is 0
．． Aromatic polycarbonates with a molecular weight of 0.1 or higher are not preferred.

Absorbance is 0. Aromatic polycarbonates of OI or higher are colored and not only have a poor initial color when molded, but are also undesirable because of their discoloration during heat resistance tests and recycling molding.

Although there are no particular limitations on the method for producing polycarbonate that does not substantially contain chlorine, the following methods may be mentioned as specific examples.

One is the method listed in JP-A-1-158033 and JP-A-1-271426.

This involves crystallizing a non-quality aromatic polycarbonate prepolymer to obtain a crystalline aromatic polycarbonate brepolymer, and solid-state polymerizing the crystalline aromatic polycarbonate prepolymer to obtain an aromatic prepolymer. It's a method.

When a non-quality aromatic polycarbonate prepolymer is produced by a transesterification method, the prepolymer is directly crystallized and subjected to solid phase polymerization to obtain an aromatic polycarbonate substantially free of chlorine.

When a non-quality aromatic polycarbonate brevolimer is produced by the phosgene method, the prebolimer is sufficiently purified and then subjected to solid phase polymerization to obtain an aromatic polycarbonate substantially free of chlorine.

In this case, the prepolymer can be easily purified because the prepolymer has a low molecular weight.

Although solid-phase silver polymerization can be carried out in the presence or absence of a catalyst, non-catalytic polymerization is preferable because the resulting polymer has much better color, heat resistance, and hot water resistance.

As the polymerization catalyst, there can be used a polymerization catalyst such as a known yuzu transesterification catalyst used for polycarbonate or polyester. Examples include alkali metal salts of bisphenol A, compounds of tin and lead, and the like.

Since the aromatic polycarbonate obtained by solid phase polymerization is a highly cohesive polymer with a high crystalline melting point and a sharp melting point peak, it is clearly distinguished from the aromatic polycarbonate produced by the conventional phosgene method or the melt method.

Since the aromatic polycarbonate of the present invention is produced by solid-phase polymerization of a crystalline aromatic polycarbonate prepolymer, the polymer is annealed during heating during solid-phase polymerization, so the melting point measured with a differential scanning calorimeter (DSC) increases, and The melting point peak is sharp. The crystal melting point (DSC peak top) is 230°C to 300°C, and the half width of the melting point peak is 3 to 8.
It is ℃.

The DSC measurement was performed under the conditions of an inert atmosphere, a temperature increase rate of 0° C./win, and a sample amount of 5 to 10 mg.

One is a method of thoroughly purifying aromatic polycarbonate obtained by the phosgene method to obtain polycarbonate that is substantially free of chlorine, as disclosed in Japanese Patent Publication No. 59-227.
No. 43 states that the chlorine content with which aromatic polycarbonate obtained by the phosgene method can be purified without using difficult steps is 0.005 to 0.2% by weight.

However, methods such as repeated extraction and purification using chlorine-free solvents, long-term vacuum drying, or treatment of polycarbonate solutions with ion exchange resins are used to remove substantially chlorine-free materials. Aromatic polycarbonates that have been purified to zero levels can be used in the present invention.

Furthermore, it is possible to obtain aromatic polycarbonates that are substantially free of chlorine atoms using the transesterification method.

However, in order to use it in the present invention, as mentioned above, it is preferable that the absorbance at 400 nm is less than 0.01. Aromatic polycarbonates with low absorbance, ie, low coloring, are also thought to cause fewer side reactions during polymerization, and are also excellent in heat resistance and hot water resistance.

The aromatic polycarbonate substantially free of chlorine atoms may be produced by any of the methods described above.

Among these, the manufacturing method using Gogawa polymerization is preferred because the manufacturing method itself is simple and the quality of the aromatic polycarbonate obtained is also good.

The molecular weight of the aromatic polycarbonate is not particularly limited as long as it can be heat-melted and molded, but the weight average molecular weight is usually 5,000 to 1,000,000, and the preferred range for molding is 10,000 to 500,000.

Phosphite diester has a structure in which two hydrogen atoms of phosphorous acid (H PH03) are substituted with hydrocarbon groups 2, and an example is R8-0 \ (in the formula, R and R9 are alkyl groups). , an aryl group, or 8 represents an alkylaryl group).

Examples of the alkyl group in the above formula include ethyl group, butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, and stearyl group. Furthermore, examples of the aryl group include phenyl group and naphthyl group.

Examples of the alkylaryl group include tolyl group, para-tertiary butylphenyl group, 2,4-ditertiary butylphenyl group, 2,6-ditertiary butylphenyl group, para-nonylphenyl group, dinonylphenyl group, etc. Can be mentioned.

Preferred specific examples include diphenyl hydrogen phosphite (R8 R9 triphenyl), bis(nonylphenyl) hydrogen phosphite (R8,R9 trinonylphenyl), bis(2,4-ditertiarybutylphenyl) hydrogen phosphite, and dicret. Examples thereof include dihydrogen phosphite, bis(p-tertiarybutylphenyl)hydrogen phosphite, bis(p-hexylphenyl)hydrogen phosphite, and the like.

In addition to those represented by the above general formula, the phosphite diester used in the present invention contains two phosphorus atoms, such as OR8/OPH (R8 is the same as above,
However, in the formula, RIO represents alkylene, arylene, or arylalkylene. ) Phosphite diesters can also be used.

Furthermore Represented by the general formula (R, Rl0 are the same as above), 8 You can also use

Among these phosphorous diesters, aromatic phosphorous diesters are preferred. Particularly preferred examples include diphenylhydrogen phosphite, bis(nonylphenyl)hydrogen phosphite, bis(2,4-di-t-butylphenyl)hydrogen phosphite, and the like.

These phosphorous acid diesters may be used alone or in a mixture.

Phosphite monoester has a structure in which one hydrogen atom of phosphorous acid (H PH03) is substituted with a hydrocarbon group 2. For example, (in the formula R
8 is the same as above).

Examples of the alkyl group in the above formula include ethyl group, butyl group, octyl group, cyclohexyl group, 2-bentylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, stearyl group, and the like. Furthermore, examples of the aryl group include phenyl group and naphthyl group.

Examples of the alkylaryl group include tolyl group, paratertiary butylphenyl group, 2,4-ditertiary butylphenyl group, 2,6-ditertiary butylphenyl group, paranonylphenyl group, dinonylphenyl group, etc. It will be done.

Preferred specific examples include phenyl dihydrogen phosphite (R8iii phenyl), nonylphenyl dihydrogen phosphite (R 8 minonylphenyl)
, 2,4-ditertiarybutylphenyl dihydrogen phosphite, and the like.

These compounds may be used alone or in mixtures.

The phenolic antioxidant has the general formula (where Rll represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or a hydrocarbon residue that may have a substituent).
may be the same or different. However, at least one of Rll represents a hydrocarbon residue which may have a substituent. ).

Specifically, 2,6-di-t-butyl-p-cresol,
2,6-di-t-butyl-p-anisole, 2,6-di-t-butyl-4-ethylphenol, 2.2'-
Methylenebis(6-t-butyl-p-cresol), 2
．． 2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-methylenebis(6-t
-butyl-0-cresol), 4.4'-butylidenebis(6-t-butyl-m-cresol), tetrakis[methylene-3-(3°,5°-di-t-butyl-4'-hydroxyphenyl)propionate]methane , 4.4'-thiobis(6-t-butyl m-
cresol), stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1.
3.5-trimethyl-2.4.6-tris(3.5-
di-t-butyl-4-hydroxybenzyl)benzene,
1,1,3-tris(2-methyl-4-hydroxy-5
-t-butylphenyl)butane, triethylene glycol bis(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate).

Preferred phenolic antioxidants have the general formula (wherein R12 is a methyl group or t-butyl group, R13 is a t-butyl group, and A is a b-valent hydrocarbon or heterocyclic residue having 1 to 30 carbon atoms). , a is an integer of 1 to 4, and b is an integer of 1 or more.)

Specifically, tetrakis [methylene-3-3〈3゜,
5゜-di-t~butyl-4'-hydroxyphenyl)
Propionate] Methane Clrganox 1010.
(manufactured by Ciba Geigy, etc.), Stearyroux β (3,5 Gt
-butyl-4-hydroxyphenyl)propionate (
Irganox 107B, manufactured by Ciba Geigy, etc.), triethylene glycol lubis (3-3-t-butyl-5
-methyl-4hydroxyphenyl)probionate and the like.

Furthermore, phenolic antioxidants containing P atoms can also be used. Specifically, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester (Irg
anox 1222, manufactured by Ciba Geigy), screws (3,
5-di-t-butyl-4τ hydroxybenzylphosphonate (ethyl)calcium (Irganox 1425WL)
, manufactured by Ciba Geigy), etc. These phenolic antioxidants may be used alone or in a mixture.

Phosphite triester has a structure in which three hydrogen atoms of phosphorous acid are substituted with hydrocarbon groups, and as an example, the general formula (wherein R lj R 15 R 16 are the same, , which may be different and represent an alkyl group, an aryl group, or an alkylaryl group).

1, the alkyl group includes an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a 2-ethylhexyl group,
Examples include decyl group, tridecyl group, lauryl group, pentaerythritol group, and stearyl group.

Examples of the aryl group include phenyl group and naphthyl group.

Examples of the alkylaryl group include tolyl group, para-tertiary butylphenyl group, 2,4-ditertiary butylphenyl group, 2,6-ditertiary butylphenyl group,
Examples include balanonylphenyl group and dinonylphenyl group.

Preferred examples include tris(2.4 ditertiarybutylphenyl)phosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, and triphenylphosphite.

(In the formula, R17, R18. R19, R20 may be the same or different and represent an alkyl group, an aryl group, or an alkylaryl group, and R21 represents alkylenearylene or arylalkylene.) Phosphite triesters can also be used.

Specific examples include tetraphenyldipropylene glycol diphosphite, tetra(tridecyl)4.4'-
Examples include isopropylidene diphenyl diphosphite.

Furthermore, a phosphorous triester represented by the formula (R17.Rl& is the same as above) can also be used.

Specific examples include bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenylpentaerythritol diphosphite, bis<2,4-di-t-butylphenyl)pentaerythritol diphosphite,
Bis(2,6-di-t-butyl-4-methylphenyl)
Examples include pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, and the like.

Furthermore, a phosphorous acid triester represented by the formula (R17.R1g, R21 are the same as above) can also be used.

A specific example is tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite.

These may be used alone or as a mixture. 2.4-ditertiarybutylphenyl group, 2
．． Those having a 6-ditertiarybutylphenyl group are
Particularly preferred specific examples for improving the hydrolysis resistance of the composition include tris(2.4-ditertiarybutylphenyl) phosphite, bis(2,4-ditertiarybutylphenyl)pentaerythritol diphosphite, Bis(2,6-ditertiarybutyl-4-methylphenyl)pentaerythritol diphosphite is mentioned.

Organic phosphonite is obtained by substituting one hydroxyl group of phosphorous acid P (OH) 3 with a hydrocarbon group, and further substituting the remaining two hydrogen atoms with hydrocarbon groups. As an example, it is represented by the formula (wherein R 22 , R 23 , and R 24 may be the same or different and represent an alkyl group, an aryl group, or an alkylaryl group). Examples of the alkyl group in the above formula include an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a decyl group, a 1.ridecyl group, a lauryl group, and a stearyl group.

Examples of the aryl group include phenyl group and naphthyl group.

Examples of the alkylaryl group include tolyl group, paratertiary butylphenyl group, 2,4-ditertiary butylphenyl group, balanonylphenyl group, dinonylphenyl group, and the like.

In addition to the above general formula, (in the formula R 25, R 26, R 27. R 28
may be the same or different, and an alkyl group,
Represents an aryl group or an alkylaryl group. R21
(same as above) is an organic phosphonite containing two phosphorus atoms.

A specific example of such a compound is 4,4'-biphenylene diphosphinic acid tetrakis (2,4-tertiarybutylphenyl).

These may be used alone or as a mixture.

The amount of one or more compounds selected from phosphite diester and phosphite monoester used is 0.0005 to 0.015 parts by weight per 100 parts by weight of aromatic polycarbonate.
ffiffi part, more preferably 0
．． The range is from 0.0005 to 0.009 parts by weight.

The amount of one or more compounds selected from phosphorous acid diesters and phosphorous acid monoesters is 0. t) If it is less than 005 parts by weight, heat resistance and hot water resistance will decrease, and 0.015 =
If it exceeds the lt part, discoloration during recycling molding and discoloration during heat resistance tests will increase, and hot water resistance will decrease. By adding l) a phenolic antioxidant to one or more compounds selected from aromatic polycarbonate, phosphite diester, and phosphite monoester, coloring in recycled molding and long-term heat aging test. It is possible to reduce coloring during the process and improve tensile elongation retention. The amount added is 0.0005 to 0.1 parts by weight, preferably 0.0005 to 0.1 parts by weight, based on 100 parts by weight of aromatic polycarbonate.
．． 0005 to 0.07 parts by weight, more preferably o. oo
t~0.05 parts by weight.

0.1! If the Ti'ffi portion is exceeded, on the contrary, coloring during the long-term heat aging test becomes intense, which is not preferable.

The effect of adding phenolic antioxidant is clear in 2 is 0.
0005 parts by weight or more.

2) By adding phosphite triester and/or organic phosphonite, composition C can reduce coloring during molding and recycling molding without reducing hot water resistance, and improve long-term heat aging resistance. can be increased by I.

The addition information is in the range of 0.0005 to 0.1 part by weight, preferably 0.0005 to 0.07 part by weight, and more preferably 0.0005 to 0.07 part by weight, per 10 g of aromatic polycarbonate.
．． 001 to 0.05 parts by weight.

If it exceeds 0.1 part by weight, hot water resistance will deteriorate, which is not preferable. The effect of addition becomes clear at 0.000! Parts by weight or more.

3) By simultaneously adding a phenolic antioxidant and a phosphorus compound selected from phosphite triesters and/or organic phosphonites, the coloring of the composition in the long-term heat aging resistance test is lower than that of the phenolic antioxidant. The amount is smaller than that of the oxidizing agent alone or the above-mentioned phosphorus compound alone, and a synergistic effect is observed, which is particularly preferable.

There is also less coloring in recycled molding.

The amount added is 0.0 parts by weight of the phenolic antioxidant and the above phosphorus compound per 100 parts by weight of the aromatic polycarbonate.
005-0.1 1ffi part, preferably 0.0
005 to 0.07 parts by weight, more preferably 0.001 to 0.07 parts by weight
It is 0.05 part by weight.

Although there is no particular restriction on the ratio of the phenolic antioxidant to the above-mentioned phosphorus compound, the range in which the synergistic effect is particularly noticeable is when the weight ratio of the phenolic antioxidant to the above-mentioned phosphorus compound is 1.
:5 to 5:l.

If the total amount added exceeds 0.1 part by weight, it is not preferable because hot water resistance deteriorates and coloration due to Changmei heat aging resistance becomes severe.

Further, the effect of addition becomes clear when the amount is 0.0005 parts by weight or more.

It is important to mix the composition of the present invention uniformly, and it is preferable to uniformly mix the composition in advance using a Henschel mixer, a Nalter mixer, a tumbler, or the like.

The composition of the present invention may be subjected to injection molding, extrusion molding, etc., as it is after mixing the respective components, but in general, 9 is pelletized through an instant extrusion machine to form a homogeneous aromatic polycarbonate composition. Used for injection molding, extrusion molding, etc.

Note that when the amount of the additive added is small, the additive may be diluted in a solvent such as acetone, added to the polymer, and then the acetone may be removed by drying.

〔Effect of the invention〕

The aromatic polycarbonate composition of the present invention has good color. There is little discoloration in heat resistance tests, and there is little deterioration in mechanical properties. There is little coloring in recycled cylindrical shapes. It is characterized by a small decrease in molecular weight and mechanical properties in hot water resistance tests. That is, the composition of the present invention is an aromatic polycarbonate composition that has excellent heat resistance, hot water resistance, and recyclability.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

11 was determined by the following method.

1. Thickness of the test piece measured by the empty CI ELAB method: 3.0 mm 2. A heat resistance test specimen (ASTM No. 4 dumbbell) was placed in a 140° C. gear oven for a predetermined period of time, and then the color and tensile elongation (ASTM D-838) of the specimen were measured.

3. Heat water resistance test: immersed in boiling water for a predetermined time and then taken out, molecular weight, tensile strength and elongation (ASTM D-638). Izod thickness 3.
0 mm (ASTMD-258) was measured.

4. Recycle test The test piece obtained by injection molding is crushed in a crusher, dried,
Perform injection molding. This cycle was repeated 5 times. The color tensile strength and elongation of the finally obtained test piece were measured.

5. Molecular weight GPC (gel permeation chromatography) [RI detector; Shodcx RI SE-51 (manufactured by Showa Denko Co., Ltd.) column; (abbreviated as Mw),
The number average molecular weight (hereinafter abbreviated as Ml) was determined by /IIl1.

6. Analysis of end groups in the prepolymer was conducted by high performance liquid chromatography or NMR analysis.

Production of Aromatic Polycarbonate 1> Production of Polycarbonate A Diphenyl carbonate was synthesized using dimethyl carbonate and phenol using lead oxide as a catalyst and the method described in Japanese Patent Publication No. 1-3181.

There were no chloride ions in the obtained diphenyl carbonate.
The content of chlorine atoms was 0.001% by weight or less.

The number average molecule ffi4100 synthesized from bisphenol A and the diphenyl carbonate has 3 terminal hydroxyl groups.
Crystalline aromatic polycarbonate prepolymer 11k with 4% terminal groups and 66% terminal phenyl carbonate groups.
g was subjected to solid phase polymerization using a 70ρ tumbler type solid phase polymerization vessel. As polymerization conditions, while injecting a small amount of nitrogen into the system, the temperature was raised from 180°C to 220°C over 6 hours under reduced pressure conditions of 1 to 2 torr using a vacuum pump.
After that, polymerization was carried out by holding at 220°C for 5 hours.
An aromatic polycarbonate with Mn = 12,500 and My = 28,000 was obtained.

The polycarbonate contains 0.00001% by weight or less of chlorine ions, and 0.00001% by weight of chlorine atoms. It was less than oot weight%.

2> Production of polycarbonate B A number-average molecule ffl4200 synthesized from bisphenol A and diphenyl carbonate with a terminal hydroxyl group of 37
Solid state polymerization was carried out in the same manner as in the preparation of polycarbonate A, except that a crystalline aromatic polycarbonate prepolymer having terminal groups of 63% was used. Mn = 13400, My = 33400
of aromatic polycarbonate was obtained.

The amount of chlorine ions in the polycarbonate is 0.00001% by weight or less, and the amount of chlorine atoms is o. It was less than oot weight%.

3> Production of polycarbonate C Diphenyl carbonate synthesized from phenol and phosgene is purified by distillation to obtain 0.00002% by weight of chlorine ions.
, a chlorine atom content of 0.001 ffi amount % or less was obtained. Using this diphenyl carbonate, solid phase polymerization was carried out in the same manner as in the production of polycarbonate A, except that a crystalline aromatic polycarbonate prepolymer having 28% terminal hydroxyl groups and 72% terminal phenyl carbonate groups was used. Ta. Mn=10100, My=2
3300 aromatic polycarbonate was obtained.

The amount of chlorine ions in the polycarbonate is 0.00002% by weight, and the amount of chlorine atoms is o. It was less than oot weight%.

4) Production of polycarbonate D Synthesized by the phosgene method.

Mn = 10800, Mw of the polycarbonate
=28000.

The chlorine ions in the polycarbonate 1 were 0.001 m% by weight, and the chlorine atoms were 0.004% by weight.

5) Production of polycarbonate E Synthesized by the phosgene method.

Mn=9200, Mv=23 of the polycarbonate
It was 000.

The chlorine ions in the polycarbonate were 0.0008% by weight, and the chlorine atoms were 0.003% by weight.

6> Production of polycarbonate F A polycarbonate was synthesized by a melt method using bisphenol A and the same diphenyl carbonate used in the production of polycarbonate C in 3). As a catalyst, sodium salt of bisphenol A was added in an amount of 5 ppm based on bisphenol A. While removing phenol from the condensate, the polymerization temperature was gradually raised from 80°C until finally reaching 310°C. The obtained aromatic polycarbonate had a number average molecular weight of 10,500 and a weight average molecular weight of 28,300.

The chlorine ions in the polycarbonate were 0.00002% by weight or less, and the chlorine atoms were 0.001% by weight or less.

1.5 g of the polycarbonate was added to 10 ml of methylene chloride.
Put it in a cell with an optical path length of 1 cm, and measure it with a spectrophotometer.
When il1 was determined, the absorbance at 400 nm was 0.013.

7) Production of polycarbonate G An aqueous solution of 64.8 g of sodium hydroxide dissolved in 800 g of water, 137 g of 2,2-bis(4-hydroxyphenol propane), 400 g of methylene chloride, and 1.7 g of phenol were mixed and emulsified. 10~20℃
Then, while stirring, 58.5 g of phosgene was gradually blown into the reactor over 1 hour to cause a reaction.

Thereafter, methyl chloroforme 1.1.
7 F! : was dissolved in 40 ml of methylene chloride, and then 6 g of phosgene was blown in for 5 minutes.
Add 0.15g of triethylamine and stir for 2 hours.
Next, the reaction mixture was branched, and the methylene chloride phase impregnated with the prebolimer was taken out and washed with 0.01N hydrochloric acid aqueous solution, thoroughly washed with distilled water until no chloride ions were detected in the washing solution, and then the methylene chloride phase was removed at room temperature. Distilled under reduced pressure with
A prepolymer was obtained containing approximately to o commercially % methylene chloride. Subsequently, this prepolymer was put into 2ρ of acetone, stirred, and then filtered to take out the prepolymer powder. Chlorine ions and chlorine atoms were detected in the washed acetone, and then washed with acetone. The obtained prepolymer was crystallized, with a crystallinity of 15% and a weight average molecular weight of 6,300.

Next, the prepolymer thus obtained was placed in a flask of a vacuum evaporator equipped with a heating furnace, and while stirring the prepolymer by rotating the flask, the temperature was raised from 190°C at a rate of 5°C/hr, and the temperature was increased from 190°C to 5°C/hr. The reaction was carried out while gradually adding mmllg of dry nitrogen under reduced pressure.

After reaching 220°C, the reaction was further carried out for 7 hours, resulting in a weight average molecular weight of 24,000 (My /Mn = 2
．． Polycarbonate 2) was obtained.

The chlorine ion content in the polycarbonate is 0.00003% by weight or less, and the chlorine atom content is 0.00003% by weight or less. It was less than oot weight%.

8> Production of polycarbonate H Bisphenol A and 0.4 mol% α,α α′ monotris(4-hydroxyphenyl′)-1.3.5-}lyisopropylbenzene and diphenyl carbonate based on bisphenol A Solid phase marketing was carried out in the same manner as in the production of polycarbonate A, except that a crystallized aromatic polycarbonate prepolymer was used.

Aromatic polycarbonate 1. with Mn = 13,000 and My = 36,000 was obtained.

The amount of chlorine ions in the polycarbonate was 0.00001% by weight or less, and the amount of chlorine atoms was 0.001% by weight or less.

9) Production of polycarbonate (2) Solid phase polymerization was carried out in the same manner as in the production of polycarbonate A, except that bisphenol A, diphenyl carbonate, and 0.0002 mol % of sodium phenolate relative to bisphenol A were used. Mn=12400
, Mw = 27900 was obtained.

The polycarbonate contained 0.00001% by weight or less of chlorine ions and 0.001% by weight or less of chlorine atoms.

10) Production of Polycarbonate J Polymerization was carried out in the same manner as in Example 1, except that diphenyl carbonate synthesized using phenol and phosgene was used after single distillation.

Mn =12400. An aromatic polycarbonate with My =27900 was obtained.

The polycarbonate contained 0.0002% by weight of chlorine ions and 0.0015% by weight of chlorine atoms.

Example 1 0.15 g of bis(nonylphenyl)hydrogen phosphite and 2.0 g of tris(2,4-ditertiarybutylphenyl) phosphite were added to 10 kg of polycarbonate A produced in 1) above. After mixing Og with a Henschel mixer, granulation was performed using an extruder. A test piece was prepared by injection molding the granulated sample. The results of the heat resistance test, hot water resistance test, and recycling test of this test piece are shown in Table 1.

Examples 2 to 7 Physical properties were evaluated in the same manner as in Example 1 using the polycarbonates shown in Table 1 and the formulations shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 3 Physical properties were evaluated in the same manner as in Example 1 using the polycarbonates shown in Table 1 and the formulations shown in Table 1. The results are shown in Table 1.

Examples 8 to 10 Comparative Examples 3 to 7 Physical properties were evaluated in the same manner as in Example 1 using the polycarbonates shown in Table 2 and the formulations shown in Table 2. The results are shown in Table 2.

Examples 11-13 Comparative Examples 8 to 12 Using the polycarbonates shown in Table 3, the physical properties were evaluated in the same manner as in Example 1 using the formulations shown in Table 3. The results are shown in Table 3.

(Hereafter the margin below)

[Brief explanation of the drawing]

FIG. 1 is a DSC chart of the aromatic polycarbonate obtained in Example 1. The polycarbonate has a melting point of 271°C and a half width of 4.3.
It was ℃.

Claims (1)

[Claims] 1. 100 parts by weight of an aromatic polycarbonate that does not substantially contain chlorine atoms, and one or more compounds selected from phosphorous acid diesters and phosphorous acid monoesters (component a) 0 .0005~0.0
15 parts by weight and 0.0005 to 0.1 part by weight of one or more compounds (component b) selected from phenolic antioxidants, phosphorous triesters, and organic phosphonites. Stabilized aromatic polycarbonate composition. 2. The composition according to claim 1, characterized in that a phosphite diester is used as component a. 3. The composition according to claim 1 or 2, characterized in that a phenolic antioxidant, a phosphite triester and/or an organic phosphonite are used as component (b). 4. The composition according to claim 1 or 2, characterized in that a phenolic antioxidant is used as component b. 5. The composition according to claim 1 or 2, characterized in that a phosphite triester is used as component b. 6. The composition according to claim 1 or 2, characterized in that an organic phosphonite is used as component b. 7. The composition according to any one of claims 1 to 6, wherein the phosphite diester is an aromatic phosphite diester. 8. The composition according to any one of claims 1 to 7, wherein the aromatic polycarbonate substantially free of chlorine atoms is a highly crystalline polycarbonate. 9. An aromatic polycarbonate containing substantially no chlorine atoms is prepared by mixing 1.0 g of the polycarbonate with 7 m of methylene chloride.
9. The composition according to claim 1, wherein the absorbance at 400 nm is less than 0.01 as measured by a spectrophotometer when the solution dissolved in 1 cm is placed in a cell with an optical path length of 1 cm. 10. One or more compounds selected from phosphorous acid diesters and phosphorous acid monoesters (component a) 0.0005 to 0.0 to 100 parts by weight of aromatic polycarbonate that does not substantially contain chlorine atoms.
15 parts by weight and 0.0005 to 0.1 parts by weight of one or more compounds (component b) selected from phenolic antioxidants, phosphite triesters, and organic phosphonites. A method for producing a stabilized aromatic polycarbonate composition. 11. The stabilized polycarbonate according to claim 10, characterized in that the aromatic polycarbonate obtained by solid-phase polymerization of a crystalline aromatic polycarbonate prepolymer is used as the aromatic polycarbonate substantially free of chlorine atoms. A method for producing an aromatic polycarbonate composition.