JPH027333B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is made of aromatic polycarbonate (mainly based on bisphenol A) with a thickness of 8 to 16 mm.
and a mixture of polyesters having butylene terephthalate, ethylene terephthalate and/or cyclohexanedimethanol terephthalate units, preferably polybutylene terephthalate units, comprising DIN 4102
Concerning products with improved flammability based on tests. Polycarbonates based on bisphenol A have advantages such as transparency, impact strength, high dimensional stability under heating, considerably reduced flammability, and good processability from the melt, e.g. by injection molding and extrusion. Has excellent physical properties. Solid bisphenol-A-polycarbonate plates with a thickness of 1 to 10 mm produced by extrusion can be used, for example, in wall panels, roofing materials, dome windows, balcony panels, schools, nurseries and Used for lagging in gymnasiums. Extruded hollow shapes made of bisphenol A polycarbonate have many applications as well. Molded articles made of bisphenol A polycarbonate do not easily combust and are classified V2 according to Underwriters Laboratories (UL) Subdivision 94, even without special flame-retardant additives. With flame-retardant additives, halogen additives or antidripping substances, the article can
Classified as V0 according to UL Subject 94. The DIN 4102 standard, which is binding in the Federal Republic of Germany, classifies building materials according to their flammability properties as follows: Building materials class A Non-flammable building materials B ₁ class Flame-retardant building materials B ₂ class Normal flammability Class B ₃ Flammable Even combustible building materials can be used on combustion shafts (Brand
-schacht) to pass this exam with a B ₁
classified; only such building materials are allowed. Bisphenol A polycarbonate plates and shapes with a thickness of 1 to 6 mm will pass the combustion shaft test if they are freshly manufactured, but will not pass after being exposed for several months. , therefore not fulfilling the requirements according to DIN 4102/B ₁ . Even with special additives, polycarbonate formulations that have been shown to be particularly flame resistant can be tested in the combustion shaft test, either immediately or after a relatively short period of outdoor exposure. I won't pass. The formulation does not meet DIN 4102-B ₁ . The present invention has a thickness of 8 to 16 mm and a thickness of 80 to 100 mm.
mol% of bisphenol A and -20 to 0 mol% of 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and/or 1,1-bis-(4-hydroxyphenyl) )--99-95% by weight of high molecular weight aromatic carbonates based on cyclohexane and 1-5% by weight of terephthalic acid with an acid component of at least 85 mol% and a diol component of at least 80 mol%. consisting of 4-butanediol, 1,2-ethanediol and/or 1,4-cyclohexanedimethanol,
Hollow chamber plates made of aromatic-aliphatic thermoplastic polyester, for example of the type according to EU-OS No. 0054856, are provided. Compared to aromatic polycarbonates, the plates have improved rheological properties and improved aging resistance. The plates pass the combustion shaft test immediately or after long-term exposure to the outside air for several years. Mixtures and applications containing polyalkylene terephthalates and polycarbonates are known (e.g. US-PS No. 3218372, DE-OS No.
No. 1694124, US-PS No. 3730767, JA No. 7401639
No., US-PS No. 3849188, DOS No. 2439342 and
DOS No. 2708381). However, plates according to the invention do not appear to be described in these publications. Polycarbonates with a thickness of 100 μm (0.1 mm) and low moisture permeability are known and are prepared from a mixture of 100 parts bisphenol A polycarbonate and 10 to 70 parts poly(tetramethylene-terephthalate) (72 Filed on December 6, 2017, August 2, 1974
Japanese publication, JP-A-49-080162; CA Vol. 82, 1975,
95 pages, Ref. 59321b; useful excerpts only). Films of polycarbonate-polyester mixtures are also known, in which bisphenol A polycarbonate 100 contains at least 10 mole percent of bis-(β
-Hydroxyethyl)-bisphenol-A ether containing a specific poly(tetramethylene-terephthalate) in a ratio of 25 to 150%.
For example, a 50 μm thick film with good mechanical strength and a sealing temperature of 150°C is described (filed on March 5, 1973, published on October 30, 1974).
JP-A No. 49-113849; CA Vol. 83, 1975, page 71, Ref. 115879z; only useful excerpts). Mixtures of polycarbonate and polyester (mixing ratio 100:1 to 100) processed into films and thin-walled products are also known, the polyester containing 20 to 100 mol% alkylene isophthalate and 80% Consisting of ~0 mol% alkylene terephthalate units (December 3, 1974)
Published on June 4, 1976, Japanese Patent Publication No. 51-064561;
CA Vol. 85, 1976, page 36, Ref. 95171y). Films and plates based on polyester-polycarbonate mixtures, consisting of at most 50% by weight polycarbonate and at least 50% by weight polyethylene terephthalate, possibly containing other additives, are also known (U.S. Pat. No. 3956229, No. 3975355 and DE-OS No.
(See No. 2647565). The flame resistance of such mixtures is
Not mentioned in these references. Polyester-polycarbonate mixtures which are stabilized by the addition of polyamides are also known (DE-OS 2751969). However, Comparative Examples A, B, D, E, F and G, which were made without polyamide, used a mixture of polycarbonate and polybutylene terephthalate (1:1 weight ratio), and Comparative Example P:
A mixture of 80 parts polycarbonate and 20 parts poly(hexamethylene-sebacate) is used. Neither of these references relates to the combustion properties of plates made of polycarbonate-polyester. Flame-resistant mixtures of polyalkylene terephthalates, organopolysiloxane-polycarbonate block copolymers and halogenated carbonate copolymers suitable for the production of films and plates are known (U.S. Pat.
(See No. 4155898). Mixtures of polyalkylene terephthalate, organopolysiloxane-polycarbonate block copolymers and calcium carbonate are also known (see US Pat. No. 4,157,997), which are suitable for the production of films and plates. Mixtures of polyesters such as certain halogen bisphenol polycarbonates and polybutylene terephthalate with improved flame retardancy are also known (see DE-OS 3023796). Finally, oriented polycarbonate films consisting of mixtures of polycarbonate and 10 to 50% by weight polyester are also known (filed Aug. 31, 1979;
Published on April 6, 1981, JP-A-56-034428; CA No.
95, 1981, 54 pages, Ref. 63445f, useful excerpts only). The high molecular weight aromatic polycarbonates according to the invention are homopolymers based on bisphenol A [2,2-bis(4-hydroxyphenyl)propane] or bisphenol A and up to 20% by weight of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl)-propane and/or 1,1
-bis-(4-hydroxyphenyl)-cyclohexane-based carbonate copolymers, or
A mixture of BPA polycarbonate and other carbonate copolymers which, in addition to bisphenol A, contains up to 20 mol% of 2,2-bis-(3,5-dimethyl-4) in the carbonate copolymer.
-hydroxyphenyl)-propane and/or 1,1-bis-(4-hydroxyphenyl)-cyclohexane. 2,2-bis(4-hydroxyphenyl) alone
Particular preference is given to polycarbonates based on propane or polycarbonate copolymers with up to 5% of two other above-mentioned diphenols. Aromatic polycarbonate is prepared by a known method.
That is, it can be prepared as described in the literature by a melt-transesterification process using bisphenol A and diphenyl carbonate and a two-phase interfacial process using bisphenol and phosgene. . The aromatic carbonate should have a relative solution viscosity of 1.26 to 1.35 in methylene chloride at 25° C. and a concentration of 0.5 g/100 ml. As is known, aromatic carbonates contain a small amount of
Preferably branched by incorporation of an amount of 0.05 to 2.0 ml % (based on the bisphenol used) of trifunctional or higher functionality compounds, especially compounds with 3 or more phenolic hydroxyl groups. be able to. Polycarbonates of this type are described, for example, in DE 1570533, DE 1595762, GB 1079821, US Pat. No. 27682 and DE 2500092. Some compounds with three or more phenolic hydroxyl groups that can be used are, for example, 2,4-bis-(hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2'-
Hydroxy-5'-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)
-2-(2,4-dihydroxyphenyl)-propane and 1,4-bis-(4,4″-dihydroxytriphenyl-methyl)-benzene. Some additional trifunctional compounds include 2, 4-
Dihydroxybenzoic acid, trimesic acid, cyanuryl chloride and 3,3-bis-(4-hydroxy-3
-methylphenyl)-2-oxo-2,3-dihydroindole (isatin-bis-cresol)
It is. The polyester according to the invention is a polyester consisting primarily of terephthalic acid and a diol selected from 1,4-butanediol, ethanediol and 1,4-cyclohexanedimethanol, preferably 1,4-butanediol. The terephthalates mentioned above, in addition to the glycol groups mentioned in the specification, contain up to 20 mol% of other groups,
i.e. aliphatic diols generally having from 3 to 12 carbon atoms or cycloaliphatic diols generally having from 6 to 21 carbon atoms, such as 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1 , 6-hexanediol, 3-methyl-2,4-pentanediol, 2-methyl-
2,4-pentanediol and 2,2,4-trimethyl-1,3-pentanediol can be included. In addition to terephthalic acid esters, up to 15 mol % of other dicarboxylic acid groups, such as isophthalic acid, adipic acid, succinic acid, sebacic acid, naphthalene-
2,6-dicarboxylic acid, diphenylcarboxylic acid,
May include azelaic acid and cyclohexane diacetic acid. Polyalkylene glycol terephthalates can be produced according to known methods, for example by transesterification of dialkyl terephthalic acid esters and the corresponding diols, e.g.
U.S. Patent Nos. 2647885, 2643989, 2534028
No. 2578660, No. 2742494 and No. 2901466
issue). For the preparation, one starts, for example, from a terephthalic acid lower alkyl ester, preferably dimethyl ester, and transesterifies the former with an excess of diol in the presence of a suitable catalyst to produce the terephthalic acid bishydroxyalkyl ester. The starting temperature of 140℃ is 210-220℃ during transesterification
rise to The released alcohol is distilled off. The condensation is then carried out at a temperature of 210 DEG -280 DEG C., while the pressure is lowered stepwise to less than 1 torr and excess diol is distilled off. The molecular weight of terephthalate is usually 30,000~
80,000, and the molecular weight w of mixed polyesters based on terephthalic acid and isophthalic acid is also usually
It is 30000-80000. w is phenol/o-
By measuring the intrinsic viscosity (intrinsic viscosity number, based on the extrapolation of the concentration of the reduced specific viscosity to zero) -IV- as a 5% solution in dichlorobenzene (1/1) at 25 °C, or RSV (reduced specific viscosity) value,
In this case, the specific viscosity can be determined by dividing the specific viscosity by the concentration of the measured solution. The above RSV values are determined using a 23% solution at 20°C in phenol-tetrachloroethane (60/40). A particularly preferred aliphatic thermoplastic polyester is polybutylene terephthalate having a pH of 30,000 to 60,000. Polycarbonate/
The polybutylene terephthalate mixture may further include heat stabilizers, antioxidants, UV stabilizers, flow aids and mold release agents. The combustion shaft test shall be conducted under the following conditions. Four test bars measuring 19 cm x 100 cm x original thickness are arranged vertically and at right angles to each other. Burn on a ring burner for 10 minutes, then turn off the burner. Combustion shaft test if the average remaining length is at least 150 mm, there are no test bars that are completely burnt out (remaining length 0 mm), and the average flue gas temperature does not exceed 200 °C. seems to pass. Before testing, the moldings are stored under normal conditions until their weight becomes constant. The test is carried out before exposure and after one or two years of exposure in the central European climate. While exposed to the outside, the test body faces south and makes a 45° angle with the ground. The polycarbonate and polyester granules can be mixed and processed into plates directly in an extruder or by preliminary homogenization in an extruder and subsequent pulverization. Reference Example Table 1 shows the test results for a solid plate with a thickness of 4 mm.

[Table] Examples Linear polycarbonate shown in note 1 of the above table,
24 months for four types of hollow chamber plates each with a thickness of 10 mm or less and a thickness of 16 mm made using the branched polycarbonate shown in Note 5 and polybutylene terephthalate with an intrinsic viscosity (IV) of 0.93 to 0.95. After exposure, a combustion shaft test according to DIN 4102 was carried out. The results were as follows. [Hollow chamber plate with a thickness of 10 mm or less] Linear polycarbonate - B1 Branched polycarbonate - B1 Mixture of linear polycarbonate and 2% by weight of polybutylene terephthalate - B1 Mixture of branched polycarbonate and 1% by weight of polybutylene terephthalate -B1 [16 mm thick hollow chamber plate] Linear polycarbonate -B2 Branched polycarbonate -B2 Mixture of linear polycarbonate and 2% by weight of polybutylene terephthalate -B1 Mixture of branched polycarbonate and 1% by weight of polybutylene terephthalate Mixture -B1

Claims (1)

[Claims] 1. A hollow chamber plate with a thickness of 8 to 16 mm,
80-100 mol% bisphenol A and 20-0 mol% 2,2-bis-(3,5-dimethyl-4-
hydroxyphenyl)-propane and/or 1,
99-95% by weight of a high molecular weight aromatic polycarbonate based on 1-bis-(4-hydroxyphenyl)-cyclohexane, and 1-5% by weight of
1,4 in which the acid component is at least 85 mol% terephthalic acid and the diol component is at least 80 mol%
- Plate consisting of an aromatic-aliphatic thermoplastic polyester consisting of butanediol, 1,2-ethanediol and/or 1,4-cyclohexanedimethanol. 2. Plate according to claim 1, characterized in that an aromatic polycarbonate based on 100 mol % of bisphenol A is used. 3. The plate according to claim 1 or 2, characterized in that polybutylene terephthalate is used as the polyester. 4. A hollow chamber plate having a thickness of 16 mm and comprising a mixture according to any one of claims 1 to 3.