JPS6038418B2 - Flame retardant polycarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aromatic polycarbonate mixed with an organic alkali metal salt, an organic alkali metal salt, or a mixture thereof, in which a sufficient amount of fluorine is added to give it unsatisfactory properties. The present invention relates to an improved flame-retardant polycarbonate composition characterized in that it contains a polyolefin compound.

There are a number of flame retardant agents available in the art that can be incorporated into polycarbonates to provide blinding or flame retardant properties.

Such flame retardants are used in a variety of applications to effectively inhibit the combustion of combustible products. But even if the polycarbonate itself doesn't catch fire, its hot particles can drip and ignite the material directly below it.

Now, we have discovered that it is possible to impart non-dripping properties to aromatic polycarbonates that have become flame retardant by mixing organic alkali metal salts, organic alkali metal salts, or mixtures thereof, by further mixing fluorinated polyolefins. discovered.

The fluorinated polyolefins used as anti-dripping agents according to the invention are commercially available or can be prepared by known methods.

It can be used, for example, at a pressure of 100-1000 psi and 0-200 psi, preferably 20-100 psi, in an aqueous medium using a free radical catalyst (e.g. sodium peroxydisulfate, potassium or ammonium).
It is a white solid obtained by polymerizing tetrafluoroethylene at a temperature of . For more information, see Brubaker US Pat. No. 2,393,967. Although not essential, relatively large particles, such as an average particle size of 0.3 to 0.7 ribs (mainly 0.7 ribs), are used.
It is preferable to use a resin in the form of particles of 5 ribs. This is 0.05~o. Better than normal polytetrafluoroethylene powder with particle size of 5 ribs. Such relatively large particle size materials are particularly preferred because they tend to disperse easily in the polymers and bind the polymers together to form fibrous materials. Such preferred polytetrafluoroethylenes are Type 3 according to ASTM.
It is actually manufactured by DuPont (E.1.
Dupont de Nemom aM Company
It is commercially available as Teflon 6 from ). The amount of fluorinated polyolefin used can vary over a wide range, but is typically from about 0.01 to about 2.0 percent (by weight) based on the total amount of resin.

The compositions of the present invention may also contain glass fibers, as described in Japanese Patent Application No. B of the same date. Furthermore, the compositions of the present invention may also contain siloxanes, as described in Japanese Patent Application C of the same date. It should be noted that these patent applications are incorporated by reference into the present invention.
Furthermore, the compositions of the present invention may also contain both glass fibers and siloxanes. The organic alkali metal salts and organic alkaline earth metal salts used in the present invention are described in detail in the following patent applications.

Victor Mark and Thomas J. Fugeboom entitled "Flame Retardant Polycarbonate Compositions" filed on December 28, 1973.
U.S. Patent Application No. 429,643 ■.

This patent application relates to a flame-retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant is a metal salt of an aromatic sulfonic acid monomer or polymer, or a mixture thereof. It can be.
U.S. Patent Application No. 429,121 to Victor Mark entitled "Flame Retardant Polycarbonate Compositions" filed December 28, 1973 and assigned to the same trustee as the present invention.
Number leg.

This patent application relates to a flame retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant is a metal salt of an aromatic sulfonesulfonic acid monomer or polymer, or a mixture thereof. could be. Victor Mark, U.S. Patent Application No. 42, entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.
No. 9642'q.

This patent application relates to a flame retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant can be a metal salt of an aromatic ketone sulfonic acid or a mixture thereof. 1973 king 12
U.S. Patent Application No. 429,166 to Victor Mark, entitled "Flame Retardant Polycarbonate Compositions," filed on May 28 and assigned to the same trustee as the present invention.

This patent application relates to flame-retardant polycarbonate compositions comprising aromatic polycarbonates incorporated with flame retardants, where the flame retardants can be metal salts of heterocyclic sulfonic acids or mixtures thereof. 1972 King December 2
8 stamp submitted and entrusted to the same trustee as the present invention.
Victor Mark U.S. Patent Application No. 429,125 {E) entitled ``Flame Retardant Polycarbonate Compositions''.

This patent application relates to a flame-retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant is an alkali metal salt of halogenated methanesulfonic acid or a mixture thereof; It can be a mixture of metal salts and alkali metal salts. Victor Mark, U.S. Patent Application No. 4296, entitled "Flame Retardant Polycarbonate Compositions," filed December 28, 1973 and assigned to the same trustee as the present invention.
No. 44'F).

This patent application relates to flame-retardant polycarbonate compositions consisting of aromatic polycarbonate incorporated with a flame retardant, where the flame retardant can be a metal salt of a halogenated non-aromatic carboxylic acid or a mixture thereof. . 197
3 Kings U.S. Patent Application No. 429,163 (G.
).

This patent application relates to flame-retardant polycarbonate compositions comprising aromatic polycarbonate incorporated with a scale flame retardant, which flame retardant may be a metal salt of an aromatic sulfide sulfonic acid or a mixture thereof. Victor Mark, U.S. Patent Application No. 429,128(H), entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention. This patent application relates to a flame retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant is a metal salt of an aromatic ether sulfonic acid monomer or polymer or a mixture thereof. could be. Victor Mark, U.S. Patent Application No. 429, entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.
No. 645 (1).

This patent application relates to flame retardant polycarbonate compositions consisting of aromatic polycarbonate incorporated with a flame retardant, where the flame retardant can be an aliphatic or olefin sulfonic acid or a mixture thereof. Victor Mark, U.S. Patent Application No. 429,126 (J), entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.
This patent application relates to flame-retardant polycarbonate compositions comprising aromatic polycarbonate incorporated with flame retardants. The descaling agent in that case may be a metal salt of a phenoester sulfonic acid monomer or polymer, or a mixture thereof. Victor Mark, U.S. Patent Application No. 429,164 (K), entitled "Flame Retardant Polycarbonate Compositions," filed December 28, 1973 and assigned to the same trustee as the present invention.

This patent application relates to flame-retardant polycarbonate compositions consisting of aromatic polycarbonates mixed with flame retardants, where the flame retardants can be metal salts of unsubstituted or halogenated oxocarboxylic acids or mixtures thereof. . Victor Mark, U.S. Patent Application No. 4291, entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.
No. 27 (L).

This patent application relates to a flame-retardant polycarbonate composition comprising an aromatic polycarbonate mixed with an elutriation agent, in which the elutriation agent is a metal salt of an aromatic carboxylic acid and a monomer or polymeric sulfonic acid of ester. or a mixture thereof. Victor Mark, U.S. Patent Application No. 429,165 (M), entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.

This patent application relates to a flame retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, which can be a metal salt of a halogenated aliphatic sulfonic acid. Victor Mark, U.S. Patent Application No. 429,646 (N), entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.

This patent application relates to a flame-retardant polycarbonate composition consisting of an aromatic polycarbonate mixed with a flame agent, where the adjacent flame agent is an aromatic amidosulfonic acid monomer;
The body may be a polymeric metal salt or a mixture thereof. Victor Mark, U.S. Patent Application No. 429, entitled "Flame Retardant Polycarbonate Compositions," filed on December 28, 1973 and assigned to the same trustee as the present invention.
No. 12 (0).

This patent application relates to a flame retardant polycarbonate composition comprising an aromatic polycarbonate mixed with a flame retardant, where the flame retardant is a metal salt of an aromatic sulfonic acid monomer or polymer or a metal salt thereof. It can be a mixture.
The above patent applications A-0 are incorporated by reference into the present invention. Any of the metal salts of any of the above patent applications and mixtures of any of the metal salts of any of the above patent applications can be used. Suitable salts include sodium 2,4,5-trichlorobenzenesulfonate, sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate,
Sodium p-iodobenzenesulfonate, sodium 4,4-dibromodiphenyl-3-sulfonate, 2,3
・Sodium 4,5,6-pentachloro-8-styrene sulfonate, sodium 4,4'-dichlorodiphenylsulfide-3-sulfonate, disodium tetrachlorodiphenyl ether disulfonate, 4,4'-dichlorobenzo Monosodium phenone-3,3'-disulfonate, sodium 2,5-dichlorothiophene-3-sulfonate, sodium diphenylsulfone-3-sulfonate, dimethyl 2,4,6-trichloro-5-sulfoisophthalate Sodium salt, 2,4,5-trichlorobenzenesulfonic acid dichloride.

Potassium salt of sulfonic acid of lophenyl, 4'-[1.4
・5.6.7.7-hexachlorobicyclo [2.2.
1]-hept-5-eneendyl]sodium benzenesulfonate, sodium hexafluorodartrate, disodium chloranilate and mixtures thereof. These salts are used in proportions of 0.01 to about 10% (by weight) based on the weight of the aromatic polycarbonate. The aromatic polycarbonates used in the practice of this invention are homopolymers or copolymers made by the reaction of dihydric phenols with carbonate precursors.

Usable dihydric phenols include bisphenols such as bis(4-hydroxyphenyl)methane, 2.2
Bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 2,2-pis(4-hydroxy-3-methylphenyl)propane, 4,4-pis(4-
hydroxyphenyl)hebutane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2.
2-bis(4-hydro.xy-3,5-dibromophenyl)propane, dihydric phenol ethers such as pis(4-hydroxyphenyl)ether, bis(3,5-dichloro-4-hydroxyphenyl)ether, etc. Dihydroxydiphenyl, such as p.p'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, etc.; 5-dimethyl-4-hydroxyphenyl) sulfone, dihydroxybenzenes such as resorcinol, hydroquinone, etc., halogen- and alkyl-substituted dihydroxybenzenes such as 1,4-dihydroxy-2.
5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc., and dihydroxydiphenyl sulfoxide such as pis(4-hydroxyphenyl) sulfoxide, bis(3,5-dipromo-4-hydroxyphenyl) sulfoxide, etc. Can be mentioned. Also, U.S. Patent Application Nos. 299, 3, 3,028,365 and 31,530
Various divalent fer/fers, such as those described in the '08 specification, can also be used for polycarbonate production.

Furthermore, the above may be combined with a halogen-containing dihydric phenol, such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. . Copolymers obtained by reacting with bread and the like are also useful for producing aromatic polycarbonates. Of course, in the production of the aromatic polycarbonate of the present invention, if a copolymer is desired rather than a homopolymer, two or more types of dihydric phenols may be used, or a dihydric phenol and a glycol, It is also possible to use hydroxy- or acid-terminated polyesters or copolymers with dibasic acids. Blends of any of the above materials may also be used in the practice of this invention to obtain aromatic polycarbonates.
The carbonate precursor used in carrying out the present invention is c.

It can be a carbonyl genide, a carbonate ester or a haloformate. Ha available. Carbonyl gesodides are carbonyl bromide, carbonyl chloride and mixtures thereof. Usable carbonates include diphenyl carbonate, di(halophenyl carbonate), di(chlorophenyl carbonate, di(promophenyl) carbonate, di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, etc.), di(alkyl carbonate), etc. phenyl), such as ditolyl carbonate,
Mention may be made of dinaphthyl carbonate, di(chloronaphthyl) carbonate, phenyltolyl carbonate, chlorophenylchloronaphthyl carbonate, or mixtures thereof. Usable haloformates include bishaloformates of dihydric phenols (bischloroformates such as hydroquinone) Z
and glycol bishalogate esters (bishalogate esters such as ethylene glycol, neobentyl glycol, and polyethylene glycol). Two preferred carbonyl chlorides are known as phosgene, although other carbonate precursors will occur to those skilled in the art. Furthermore, polymers of dihydric phenols, dicarboxylic acids and carbonic acids are also included.

Such materials are described in US Pat. No. 3,169,121, which is hereby incorporated by reference. The polycarbonates of this invention are produced by the use of molecular weight modifiers, acid acceptors and catalysts.

Molecular weight modifiers that can be used in the practice of the present invention include phenol, cyclohexanol, methanol, p-
Examples include ten-butylphenol and p-bromophenol. Preferably, phenol is used as molecular weight regulator. Suitable acid acceptors may be organic or inorganic acid acceptors.

Suitable organic acid acceptors are tertiary amines, examples of which include pyridine, triethylamine, dimethylaniline, tributylamine, and the like. Suitable inorganic acid acceptors may also be alkali metal or alkali metal hydroxides, carbonates, bicarbonates or phosphates. It will be appreciated that other types of materials can also be used with the aromatic polycarbonates of the present invention, such as antistatic agents, pigments, template agents, heat stabilizers, UV stabilizers, reinforcing agents, etc. Examples include fillers.
In preparing the composition of the present invention, an aromatic polycarbonate may be mixed with an organic alkali metal or alkali metal salt and a fluorinated polyolefin. In order that those skilled in the art may more clearly understand the principles and implementation of the present invention,
Examples are shown below.

When parts or percentages are mentioned, it is by weight unless otherwise stated. Example 1
A polycarbonate composition was prepared.

First, essentially equimolar amounts of 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and phosgene are prepared in an organic medium under standard conditions using triethylamine, sodium hydroxide, and phenol. By reacting, a homopolymer of bisphenol A was produced. The polymer thus obtained was fed to an extruder operated at about 26,500 mph and the extrudate was subdivided into pellets. Approximately 31 pellets
Approximately 5 inches long x 1 wide by injection molding with yC
/2 inch x approximately 1/16 to 1/8 inch thick specimens were prepared.

Such test pieces (5 pieces for each additive in Table 1 below)
On the other hand, Underwriter Laboratory (Underwrite)
eR Laboratones, lm. ) Publication 94 “Flammability Test for Material Classification” (hereinafter referred to as UL-94)
The test procedures described therein were carried out.

If you follow this test procedure, based on the performance of the five test pieces,
Material is UL-94V-0, UL-94V-1 or UL
-Rated as Shigeru V-ro. Each V by UL-Hiroshi
The evaluation criteria can be summarized as follows. “UL
-94V-0'' - When the average time of flaming and/or flameless combustion after removal of the ignition flame does not exceed 5 seconds and no particles drip from the test piece and ignite the absorbent cotton. "UL-94V-1" - If the average time of flaming and/or flameless combustion after removal of the ignition flame does not exceed 29 seconds, and particles do not drip from the test piece and ignite the degreasing rope. .

"UL-94V-D" When the average time of flaming and/or flameless combustion after one ignition flame is removed does not exceed 29 sand, and particles that flammably burn drop from the test piece and ignite the absorbent cotton.

Furthermore, specimens that continue to burn for more than 29 stages after removal of the ignition flame are classified as "burning" (according to the standards of the present invention rather than UL-94).

Note that in order to give a specific V rating according to UL-94, all test specimens must satisfy that standard. Otherwise, the five specimens will be evaluated by the worst performing one among them. For example, if one test piece is classified as UL-94V-0 and the remaining four test pieces are classified as UL-94V-0, the evaluation for the five test pieces is UL-94V-D. The results are shown in Table 1 below.

Example 2 Into the polycarbonate of Example 1, 0.5 part of sodium 2,4,5-trichlorobenzenesulfonate was added.

Such a mixture was extruded as in Example 1,
Molded and tested. Example 3 In the polycarbonate of Example 1, 0.5 parts of sodium 2,4,5-trichlorobenzenesulfonate and 0.05 parts of poly(tetrafluoroethylene) (sold as Teflon 6 by DuPont) were added. added.

Such a mixture was extruded as in Example 1,
Molded and tested. The remaining compositions were also the same as those from Example 1.
It was prepared according to method 3.

Table 1 As can be seen from the data in Table 1, when the polycarbonate composition contains the fluorinated polyolefin at the same time as the retardant, no particle dripping occurs and the composition therefore
-94V-0 or UL-94V-1.

Similar results can be obtained using other elutriation agents and fluorinated polyolefins in place of those shown in Table 1.

Example 19, 1 to 3 melons, 3 dishes Other compositions were prepared, extruded, molded and tested as in Example 1 with the results shown in Table 2.

TABLE 2 It will thus be seen that the aforementioned objectives, including those which will become apparent from the foregoing description, are effectively achieved.

Claims (1)

[Claims] 1 Metal salts of aromatic sulfonic acid monomers and polymers, metal salts of aromatic sulfonesulfonic acid monomers and polymers, metal salts of aromatic ketone sulfonic acids, metal salts of heterocyclic sulfonic acids, halogenated Metal salts of methanesulfonic acid, metal salts of halogenated non-aromatic carboxylic acids, metal salts of aromatic sulfide sulfonic acids, metal salts of aromatic ethersulfonic acid monomers and polymers, aliphatic or olefin sulfonic acids metal salts of phenol ester sulfonic acid monomers and polymers, metal salts of unsubstituted or halogen-substituted oxocarboxylic acids, metal salts of sulfonic acids of aromatic ester monomers and polymers, halogenated resins Organic alkali metal salts, organic alkaline earth metal salts, or mixtures thereof selected from metal salts of cyclic aromatic sulfonic acids and metal salts of aromatic amidosulfonic acid monomers and polymers, or a mixture thereof, by weight of aromatic polycarbonate. in a non-halogenated aromatic polycarbonate made flame retardant with the addition of 0.01 to 10% by weight, based on the weight of the aromatic polycarbonate, and in addition 0.01 to 2.0% by weight, based on the weight of the aromatic polycarbonate, of ASTM Type 3 polycarbonate. A polycarbonate composition characterized in that it is made non-dripping by adding tetrafluoroethylene.