JPH02247248A - Polycarbonate composition - Google Patents

Abstract

PURPOSE:To obtain a composition having improved melt stability by mixing aromatic polyester and specific aromatic polycarbonate in a specific ratio. CONSTITUTION:(A) 1-90wt.%, preferably 20-80wt.% aromatic polyester [e.g. poly(1,4-butylene terephthalate)] is mixed with (B) 99-10wt.%, preferably 80-20wt.% aromatic polycarbonate containing phenolic terminal group expressed by formula I and non-phenolic terminal group expressed by formula II (R1 and R2 are H or <=20C alkyl, may be substituted by halogen) in a ratio of >=1/19, preferably 1/5-1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition containing an aromatic polyester and an aromatic polycarbonate, and its purpose is to improve the melt stability.

[Conventional technology 1] In order to take advantage of the excellent moldability and chemical resistance of aromatic polyesters such as polyethylene terephthalate and polyethylene terephthalate, and the excellent impact resistance and high glass transition temperature of aromatic polycarbonate, both resins were used. It is known to mix (JP-A-48-54160 and JP-A-49-107354).

[Problems to be Solved by the Invention] However, molded products made from compositions of aromatic polyester and aromatic polycarbonate have poor melt stability and have a problem in that their Vicat softening point decreases during deferred molding. be.

[One Means for Solving the Problems] The present inventor has improved the melt stability of a composition of aromatic polyester and aromatic polycarbonate by changing the ratio of the end groups of aromatic polycarbonate to a different ratio than before. We found that there was a significant improvement.

That is, the present invention uses 1 to 90% by weight of aromatic polyester.
and a resin composition containing 99 to 10% by weight of aromatic polycarbonate, the aromatic polycarbonate has a phenolic terminal group represented by the following formula (I>) and a phenolic terminal group represented by the following formula (
The ratio to the non-phenolic end group shown in II) is 171
9 or more (R1 and R2 can be the same or different from each other and are each a hydrogen atom or an alkyl group having 20 or less carbon atoms) , which may be substituted with halogen).

Adjustment of the terminal @ group ratio of aromatic polycarbonate can be easily carried out by producing aromatic polycarbonate by a transesterification method and changing the molar ratio of the raw materials diphenyl carbonate and diphenol (e.g. bisphenol A) at that time. . In the present invention, the aromatic polycarbonate has the formula % (each R is phenylene, halogen-substituted phenylene or C1
~2o Alkyl-substituted phenylene, A and B represent a hydrogen atom, a C1-12 hydrocarbon group containing no aliphatic unsaturation, or a group that forms a cycloalkane group together with adjacent carbon atoms; Mainly have. For example, when bisphenol A and diphenyl carbonate are transesterified, the terminals of the polycarbonate are phenolic residues derived from bisphenol A or phenyl groups derived from diphenyl carbonate. Therefore, increasing the molar ratio of bisphenol A during the transesterification reaction increases the proportion of phenolic end groups in the polycarbonate produced. Note that aromatic polycarbonate may be branched. Such branched polycarbonates combine polyfunctional aromatic compounds with diphenols and/or
Alternatively, branched thermoplastic random branched polycarbonates can be obtained by reacting with carbonate precursors.

In aromatic polycarbonates commonly used in the past, especially aromatic polycarbonates made by the phosgene method, the ratio of phenolic end groups to non-phenolic end groups is 1720 or less.

That is, polycarbonate is produced by reacting bisphenol A and phosgene, and by adding a small amount of phenol to the raw materials or during the reaction, the polymer terminals are capped with phenol (hydroxyl groups react).

By adjusting the ratio of the phenolic end groups of the aromatic polycarbonate according to the invention to 1719 or more, preferably 1710 or more, especially 175 or more, up to Ilo, the melt viscosity of the composition of this and the aromatic polyester is significantly improved. .

The degree of opening (OH group of the phenolic terminal group) is 36 in FTIR.
The total end group concentration is calculated by determining the average molecular weight based on the IV (intrinsic viscosity) value measured in methylene chloride solution. IV value When converting to the average molecular weight, the 5 channel formula was used.

-40,83 IV=1.23x10 M (M=viscosity average molecular weight) The aromatic polyester used in the present invention is not particularly limited, but specifically, aromatic dicarboxylic acid or its derivative and dihydric alcohol or dihydric Polycondensation polyester obtained from a phenol compound, polycondensation polyester obtained from a dicarboxylic acid or its derivative and a cyclic ether compound, polycondensation polyester obtained from a metal salt of a dicarboxylic acid and a dihalogen compound, ring-opening polymerization of a cyclic ester compound. Examples include polyester according to The term "acid derivative" as used herein refers to acid anhydrides, esters, and acid chlorides. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, etc., and preferably terephthalic acid, isophthalic acid, or a mixture thereof.

Examples of dihydric alcohols include ethylene glycol,
Examples include propylene glycol, butane-1,4-diol, hexamethylene glycol, etc., and preferably ethylene glycol and butane-1,4-diol. Examples of dihydric phenol compounds include bisphenol A, resorcinol, and the like. Examples of cyclic ether compounds include ethylene oxide,
Examples include propylene oxide. Furthermore, examples of the cyclic compound include ε-caprolactone and the like. The dihalogen compound to be reacted with the dicarboxylic acid metal salt refers to a compound obtained by replacing two hydroxyl groups of the dihydric alcohol or dihydric phenol compound with halogen atoms such as chlorine or bromine.

As the polyester, poly(1,4-butylene terephthalate) and polyethylene terephthalate are particularly preferably used.

In the present invention, the quantitative ratio of aromatic polyester and aromatic polycarbonate is 1 to 90% by weight and 99 to 10% by weight, respectively, preferably 20 to 80% by weight and 80 to 20% by weight, respectively.
Weight%. If one of them is less than the above, the desired physical properties thereof will not be exhibited.

Furthermore, the resin composition material of the present invention may contain other resins, additives, such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weatherproofing agents, etc., during resin mixing and molding, as long as the physical properties are not impaired. Agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, etc. can be added.

Reinforcing fillers include finely divided aluminum, iron or nickel, metal oxides and non-metals, e.g. carbon filaments, silicates, e.g. mica, aluminum silicates (clays).
, talc, asbestos, titanium dioxide, wollastonite, tubaculite, potassium titanate and titanate whiskers, glass flakes, glass peas and glass fibers, and polymer fibers, or combinations thereof.

The reinforcing filler may be used in an amount sufficient to exhibit a reinforcing effect, but it is usually 1 to 60% by weight of the total weight of the composition.

A preferred range is 5-50% by weight.

A suitable reinforcing agent is glass, for example glass filaments or mixtures of glass and talc, glass and mica, glass and aluminum silicate are preferably used. Filaments for plastic reinforcement are preferably produced by mechanical tension.

The diameter of the gas filament is approximately 0.00012~0.00
075 inches is preferred, but this is not essential to the invention.

If the composition of the invention comprises a polycarbonate consisting of brominated bisphenols, inorganic or organic antimony compounds may be further incorporated into the composition of the invention in order to synergistically enhance the flame retardancy achieved thereby. Suitable inorganic antimony compounds include antimony oxide (Sb203):antimony phosphate;KSb(OH)6:NH45b)-
6:5bS3: etc. A wide variety of organic antimony compounds may also be used, such as antimony esters with rad, cyclic alkyl antimonites, aryl antimonites, and the like. Examples of typical organic antimony compounds are KSb tartrate, sb caproate, Sb
b (OCH2CH3): Sb [0C1-1(CH
3) CH2CH3]3; Includes Sb polymethylene glycolate, triphenylantimony, and the like. Use antimony compounds. In this case, the preferred antimony compound is antimony oxide.

Hindered phenols, phosphites, metal phosphates, metal phosphites, etc. can be mixed as stabilizers and antioxidants.

When producing the resin composition of the present invention, each component can be mixed by a conventionally known method. For example, a method may be appropriately selected in which the components are dispersed and mixed using a high-speed mixer such as a turnpull mixer or a Henschel mixer, and then melt-kneaded using an extruder, a Banbury mixer, a roll, or the like.

"Example" In the following examples, "parts" refer to parts by weight.

The aromatic polycarbonate according to the present invention used in the examples was obtained by transesterifying diphenyl carbonate and bisphenol Δ, and the intrinsic viscosity measured at 25°C in methylene chloride was 0.51 CII/g. . The ratio of phenolic to non-phenolic end groups was 1/9, 3.7 and 9/1. these are,
It was made by varying the molar ratio of diphenyl carbonate and bisphenol A. These are respectively P C (
10), p C (30) and P C (90).

For comparison, an aromatic polycarbonate (Le
Xa Old 41, trademark, General Electric Co., intrinsic viscosity at 25°C in methylene chloride 051 dl/g) was used. This is expressed as P C (1).

Polybutylene terephthalate (Valox 315, trademark, General Electric Company) was used as the aromatic polyester. This is expressed as PBT.

The melt viscosity of the resin composition was measured using a capillary melt viscometer (Cabilograph) manufactured by Toyo Seiki Seisakusho, Tokyo. This device consists of a heating cylinder and an orifice of the same dimensions as the melt index measuring device described in ASTH-01238. After preheating the resin sample, at the capillary wall 6 s−1
is passed through the capillary orifice with a piston driven by mechanical means at a constant speed selected to provide a shear rate of .

The melt viscosity is maintained at 250'C or 280°C during the measurement. The force applied to the piston is measured by a load cell and recorded continuously on a strip chart. Melt viscosity is calculated from the force on the piston and the shear rate at the capillary wall. The Vicat softening point was measured under the following conditions according to AST) I-01525.

Heating rate 120'C/h Test piece 1/8"Xi/2"X2.5°"Example 1 and Comparative Example 1 40 parts of PBT and 60 parts of PC(30) or PC(1)
The components were mixed in a Henschel mixer and then extruded in an 85 m single screw extruder to form a pelletized composition.

Next, the pellets were dried and kept at 270° C. for a predetermined period of time, after which the melt viscosity was measured. The results are shown in Table 1.

Table 1 Comparative Example 1 Example PBT (parts) 40 40PC(
1) (Part) 60 After staying in the pond for 5 minutes 4100 400010
After residence for 6400 minutes 3300 After residence for 20 minutes 3000 3100 After residence for 30 minutes 2600 3000 In Comparative Example 1 using PC (1) with fewer phenolic end groups, the melt viscosity increased once and then suddenly decreased.

On the other hand, in Example 1 using PC(30) with many phenolic end groups, the melt viscosity only gradually decreased and remained stable.

Examples 2 to 4, Comparative Example 2 40 parts of PBT and PC (1), PC (10), PC
Pellets were made in the same manner as in Example 1 from 60 parts of PC(30) or PC(90).

Using each pellet, a test piece (1) was made in the usual manner using an extrusion molding machine set at a cylinder temperature of 270°C. Further, the molten composition was allowed to stay in the molding machine for 15 minutes, and then extruded in the same manner to produce a test piece (2).

The throat softening points of test pieces (1) and (2) were measured. The results are shown in Table 2.

BT PC (1) PC (10) PC<30) PC (90) Vicat softening point test piece (1) Test piece (2) In difference comparison example 2, the throat softening point of test piece (2) was significantly lowered. , the difference between test pieces (1) and (2) is also large.

On the other hand, in Examples 2 to 4, the difference between test pieces (1) and (2) was small, and a stable softening point was achieved.

Applicant: Japan GE Plastics Co., Ltd.

Claims (1)

[Scope of Claims] In a resin composition containing 1 to 90% by weight of aromatic polyester and 99 to 10% by weight of aromatic polycarbonate, the aromatic polycarbonate contains a phenolic end group represented by the following formula (I) and the following formula: A resin composition characterized by containing an aromatic polycarbonate having a ratio of 1/19 or more to the non-phenolic end group represented by (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ Mathematical formula , chemical formulas, tables, etc.▼(II) (R_1 and R_2 can be the same or different from each other,
each of which is a hydrogen atom or an alkyl group having up to 20 carbon atoms and may be substituted with halogen).