JP2719486B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame retardant polycarbonate (hereinafter abbreviated as PC) resin composition.

[0002]

2. Description of the Related Art PCs are widely used in many fields such as OA equipment, home appliances, machinery, and construction because of their transparency and excellent impact strength. This PC has self-extinguishing properties and is also preferable as various materials from this point of view. However, in order to satisfy safety requirements in various applications, a PC resin composition with further enhanced flame retardancy ( Hereinafter, the development of a flame-retardant PC resin composition) is strongly demanded.

As the flame-retardant PC resin composition, aromatic P
There is a compound obtained by adding potassium perfluoroalkanesulfonate to C (see Japanese Patent Publication No. 47-40445). However, since this flame-retardant PC resin composition is easy to drip once burned, the viewpoint of preventing fire spread. Is still insufficient. For this reason, it is difficult to drip even if it burns.
As the C resin composition, a composition in which an organic alkali (earth) metal salt is mixed with aromatic PC and siloxane is further added has been developed (see Japanese Patent Publication No. Sho 60-16473).

[0004]

However, the flame-retardant PC resin composition obtained by mixing an aromatic PC with an organic alkali (earth) metal salt and further adding siloxane has a drawback that transparency is low. There is. An object of the present invention is to provide a flame-retardant PC resin composition which is hard to drip even when burned and has high transparency.

[0005]

The flame-retardant PC resin composition of the present invention that achieves the above object comprises an aromatic polycarbonate and an alkali (earth) perfluoroalkanesulfonate.
A metal salt and an organic siloxane having an alkoxy group, a vinyl group and a phenyl group are contained as essential components, and the ratio of the alkali (earth) metal salt of perfluoroalkanesulfonic acid to 100 parts by weight of the aromatic polycarbonate is 0.1%. Wherein the ratio of the organosiloxane is from 0.05 to 2.0 parts by weight.

Hereinafter, the present invention will be described in detail. There are various aromatic PCs as one of the essential components in the flame-retardant PC resin composition of the present invention. For example, general formula (I)

Embedded image (Wherein, R ¹ and R ² are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, which may be the same or different. When m is 2 to 4, R ¹ may be different from each other, and when n is 2 to 4, R ² may be different from each other Z is a single bond, carbon C1-C8 alkylene group, C2-C8 alkylidene group, C5-C15 cycloalkylene group, C5-C5
15 cycloalkylidene group or -SO ₂ -, - SO
-, -S-, -O-, -CO- bond or the general formula (I
I)

Embedded image The bond represented by is shown. Various polymers having a repeating unit represented by the formula (1) are exemplified. Further, its viscosity average molecular weight is 100% from the viewpoint of mechanical strength and moldability.
It is preferably from 100 to 100,000, and particularly preferably 150
It is preferably from 00 to 40,000.

The aromatic PC may be one or more of homopolymers obtained by using one kind of dihydric phenol, or a copolymer obtained by using two or more kinds of dihydric phenol. Or one or more of these. Further, one or more thermoplastic random branched PCs obtained by using a polyfunctional aromatic compound together with a dihydric phenol may be used. Furthermore, a mixture using at least two of these homopolymers, copolymers, and thermoplastic random branched PCs may be used.

[0008] Such an aromatic PC is prepared by, for example, preparing a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, with one or more dihydric phenols and a carbonate such as phosgene. By reaction with the precursor,
Alternatively, it is produced by a transesterification reaction of one or more dihydric phenols with a carbonate precursor such as diphenyl carbonate. When a thermoplastic random branched PC is obtained, a polyfunctional aromatic compound is added to the reaction system as described above.

Here, as the dihydric phenol, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,2-bis (4-hydroxyphenyl) ethane,
3,3-bis (4-hydroxyphenyl) pentane,
1,1- (4-hydroxyphenyl) cyclohexane,
4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether,
4,4'-dihydroxybenzophenone and the like. Alternatively, 2,2-bis (3,5-dibromo-4-
Hydroxyphenyl) propane, 2,2-bis (3,5
-Dichloro-4-hydroxyphenyl) propane, 2,
Examples thereof include halogenated bisphenols such as 2-bis (3-chloro-4-hydroxyphenyl) propane and 2,2-bis (3-bromo-4-hydroxyphenyl) propane. Among these dihydric phenols, bisphenol A is particularly preferred.

The polyfunctional aromatic compound used as a branching agent for obtaining a thermoplastic random branched PC includes phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, gallic acid n -Propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, trimellityl chloride, isatin bis (o-cresol), trimellityl trichloride, 4-chloroformyl phthalate Acid anhydride, benzophenonetetracarboxylic acid, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2' , 4,4'-Tetrahydroxyphenyl ether 2,4,4'-trihydroxydiphenyl-2-propane, 2,2'-bis (2,4
-Dihydroxy) propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 1- [α-methyl-α-
(4′-hydroxyphenyl) ethyl] -3- [α ′,
α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ) Ethyl] benzene, α, α ', α "-
Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2′-hydroxy-5′-methylbenzyl) -4-methylphenol,
4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-
2,4,6-tris (4'-hydroxyphenyl) -2
-Heptane, 1,3,5-tris (4'-hydroxyphenyl) -benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4'- (Hydroxyphenyl) cyclohexyl] -propane, 2,6-bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) ) -5-Methylphenyl] methane, bis [2-hydroxy-3- (2′-hydroxy-5′-isopropylbenzyl) -5-methylphenyl] methane,
Tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ′,
4 ', 7-trihydroxyflavan, 2,4,4-trimethyl-2', 4 ', 7-trihydroxyflavan,
1,3-bis (2 ', 4'-dihydroxyphenylisopropyl) benzene, tris (4'-hydroxyaryl) -amyl-s-triazine and the like.

The flame-retardant PC resin composition of the present invention comprises an alkali (earth) metal salt of perfluoroalkanesulfonic acid as an essential component other than the aromatic PC.
It is contained at a ratio of 0.03 to 0.3 parts by weight with respect to 0 parts by weight. Here, the “alkali (earth) metal salt of perfluoroalkanesulfonic acid” is defined by the formula (III)

Embedded image (Where n represents an integer of 1 to 10, M represents an alkali metal or an alkaline earth metal, and m represents the same integer as the valency of M). The alkali (earth) metal salt of perfluoroalkanesulfonic acid may be used alone or in combination of two or more.

Specific examples of perfluoroalkanesulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, and perfluorohexanesulfonic acid. , Perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc., and particularly, the number of carbon atoms [formula (III)
In which n is 1 to 8.

Specific examples of the alkali metal or alkaline earth metal represented by M in the above formula (III) include:
Examples thereof include lithium, sodium, potassium, cesium and the like (alkaline metal), magnesium, calcium, strontium, barium and the like (alkaline earth metal), with potassium being particularly preferred.

The reason for limiting the proportion of the alkali (earth) metal salt of perfluoroalkanesulfonic acid to 0.03 to 0.3 parts by weight based on 100 parts by weight of aromatic PC is as follows.
If the amount is less than 0.03 part by weight, it is difficult to achieve the target flame retardancy [one that conforms to V-0 of UL94 combustion test (1/12 inch)]. If the amount exceeds the above range, further improvement of the flame retardancy cannot be expected, and also, the resulting flame retardant PC resin composition causes a decrease in physical properties such as impact strength and a decrease in transparency. A desirable ratio of the alkali (earth) metal salt of perfluoroalkanesulfonic acid is aromatic PC 1
It is 0.1 to 0.2 parts by weight with respect to 00 parts by weight.

The flame-retardant PC resin composition of the present invention comprises an alkoxy group, an essential component other than aromatic PC and an alkali (earth) metal salt of perfluoroalkanesulfonic acid.
The organic siloxane having a vinyl group and a phenyl group is used in an amount of 0.05 to 2.0 based on 100 parts by weight of the aromatic PC.
It is contained in parts by weight. In this organosiloxane, the silicon at the terminal of the main chain or side chain of the siloxane bond has an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group. In addition to having a vinyl group, two bonds of silicon in the molecule are substituted with a phenyl group at an arbitrary ratio. One or more organic siloxanes may be used.

The ratio of the organic siloxane is determined by the aromatic PC
The reason for limiting the amount to 0.05 to 2.0 parts by weight with respect to 100 parts by weight is that if it is less than 0.05 part by weight, it becomes difficult to prevent dripping during combustion, and 2.0 parts by weight is used. If the amount exceeds the above range, further improvement in the effect of preventing dripping cannot be expected, and also the resulting flame-retardant PC resin composition will have reduced physical properties such as impact strength. A desirable ratio of the organic siloxane is 0.1 to 0.5 parts by weight based on 100 parts by weight of the aromatic PC.

The flame-retardant PC resin composition of the present invention comprises the aromatic PC described above, an alkali (earth) metal salt of perfluoroalkanesulfonic acid, and an organic siloxane having an alkoxy group, a vinyl group and a phenyl group. Although it is an essential component, various additives as necessary, for example, various additives including inorganic fillers, other synthetic resins,
An elastomer or the like can be contained within a range that does not impair the object of the present invention.

The above-mentioned inorganic filler is blended for the purpose of improving or increasing the mechanical strength and durability of the resin composition. Specific examples thereof include glass fibers, glass beads, glass flakes, carbon black, and sulfuric acid. Calcium, calcium carbonate, calcium silicate, titanium oxide,
Examples include alumina, silica, asbestos, talc, clay, mica, and quartz powder. Specific examples of the additives include antioxidants such as hindered phenols, phosphites, phosphates, and amines; ultraviolet absorbers such as benzotriazoles and benzophenones; and hindered amines. Light stabilizers, external lubricants such as aliphatic carboxylic acid esters and paraffins, common flame retardants, release agents, antistatic agents, coloring agents and the like.

Specific examples of the synthetic resin include aliphatic polycarbonate, polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin (AS resin), acrylonitrile / butadiene / styrene resin (ABS resin), polymethyl methacrylate, polyethylene terephthalate, Butylene terephthalate, polyamide and the like. Specific examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, and polyamide elastomer.

The flame-retardant PC resin composition of the present invention can be obtained by mixing and kneading the above-mentioned three essential components with various additional components used as required.
The compounding and kneading at this time may be performed by a conventional method using, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneder, a multi-screw extruder, or the like. The heating temperature during kneading is usually selected from the range of 240 to 300 ° C.

The thus obtained flame retardant P of the present invention
The C resin composition is hard to drip even when burned, and has high transparency, and can be formed by various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calender molding, and rotational molding. It can be formed into a desired shape and used in various fields.

[0022]

Embodiments of the present invention will be described below. Example 1 Linear PC as an aromatic PC [manufactured by Idemitsu Petrochemical Co., Ltd .:
A2500. Hereinafter, it is abbreviated as linear PC. ], And perfluoroalkanesulfonic acid alkali (earth) F1 of C ₄ F ₉ SO ₃ K [Dainippon Ink Chemical Co., Ltd. as a metal salt
14 (trade name)] and KR219 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter referred to as organic siloxane A) as an organosiloxane having an alkoxy group (methoxy group), a vinyl group, and a phenyl group. After drying these, C ₄ F _{9 was} added to 100 parts by weight of linear PC.
0.1 parts by weight of SO ₃ K and 0.3 parts by weight of organic siloxane A were respectively blended and supplied to an extruder.
The mixture was kneaded at 80 ° C. to obtain a pellet-shaped flame-retardant PC resin composition.

The flame-retardant PC resin composition is heated at 120 ° C. for 1 hour.
After drying for 2 hours, injection molding was performed at a mold temperature of 80 ° C. to obtain test pieces, and the following evaluation was performed using these test pieces. Oxygen index Measured according to JIS K7201. Flammability Complies with UL94 combustion test (1/12 inch) (hereinafter, 1
/ 12UL94) or UL94 combustion test (1/16 inch) (hereinafter abbreviated as 1 / 16UL94). Number of drops during combustion According to the UL94 combustion test (1/12 inch or 1/16 inch), the total number of drops dropped from each test piece until the five test pieces extinguished (hereinafter, five drops of the test) Abbreviated as a number).

Haze Measured according to JIS K7105 (thickness: 3 mm).
Table 1 shows the results.

Examples 2 and ₃ Example 1 was repeated except that the amounts of linear PC, C ₄ F ₉ SO ₃ K and organosiloxane A were set to the proportions shown in Table 1, respectively.
In the same manner as in the above, flame-retardant PC resin compositions were obtained.
Each of the flame-retardant PC resin compositions was evaluated in the same manner as in Example 1 above. Table 1 shows the results.

Example 4 As the aromatic PC, the aforementioned linear PC and thermoplastic random branched PC [Idemitsu Petrochemical Co., Ltd .: IB 2500. Less than,
Abbreviated as branch PC. ], 60 parts by weight of the former and 40 parts by weight of the latter are used.
A flame-retardant PC resin composition was obtained in the same manner as in Example 1, except that the proportions of C ₄ F ₉ SO ₃ K and organosiloxane A were each 0.1 parts by weight with respect to 00 parts by weight. And about the obtained flame-retardant PC resin composition,
Was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 Flame retardancy was performed in the same manner as in Example 1 except that the ratio of C ₄ F ₉ SO ₃ K to 100 parts by weight of the linear PC was 0.2%, and the organic siloxane A was not used. A reactive PC resin composition was obtained. And about the obtained flame-retardant PC resin composition, evaluation of said-was performed like Example 1. Table 1 shows the results.

Comparative Example 2 Instead of the organic siloxane A, an organic siloxane having only a phenyl group [KF56 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.]. Hereinafter, it is referred to as organic siloxane B. ] Was used in the same manner as in Example 2 except that 0.3 parts by weight was used to obtain a flame-retardant PC resin composition. And about the obtained flame-retardant PC resin composition, evaluation of said-was performed like Example 2. Table 1 shows the results.

Comparative Example 3 Organosiloxane having only methoxy group instead of organosiloxane A [KF851 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] Hereinafter, it is referred to as organic siloxane C. ] Was used in the same manner as in Example 1 except that 0.3 parts by weight was used to obtain a flame-retardant PC resin composition. And about the obtained flame-retardant PC resin composition, evaluation of said-was performed like Example 1. Table 1 shows the results.

Comparative Example 4 C ₄ F ₉ per 100 parts by weight of aromatic PC (linear PC)
A flame-retardant PC resin composition was obtained in the same manner as in Example 1, except that the proportion of SO ₃ K was set to 0.5 part by weight, which was out of the range of the present invention. And about the obtained flame-retardant PC resin composition, evaluation of said-was performed like Example 1. Table 1 shows the results.

Comparative Example 5 A flame-retardant PC resin composition was obtained in the same manner as in Example 4 except that the organosiloxane A was not used. And about the obtained flame-retardant PC resin composition, evaluation of said-was performed like Example 4. Table 1 shows the results.

[0032]

[Table 1]

As is clear from the comparison between the evaluation results of Examples 1 to 3 and the evaluation results of Comparative Example 1 shown in Table 1,
In the case of containing organic siloxane A, the oxygen index is improved and dripping during combustion is prevented, and the flame retardancy is improved.
As is clear from the haze value, the decrease in transparency is small. Further, as is apparent from the evaluation results of Example 4, by using a combination of a linear PC and a thermoplastic random branched PC as the aromatic PC, the flame retardancy is further improved without lowering the transparency. be able to.

On the other hand, as is clear from the evaluation results of Comparative Examples 1 to 3 and Comparative Example 5, those containing no organic siloxane A were thermoplastic random branched P
Drops occur during combustion regardless of the use of C. In addition, as is clear from the evaluation results of Comparative Example 2, those containing organosiloxane B have a small decrease in transparency but are insufficient in improving the oxygen index and preventing dripping during combustion. And as is clear from the evaluation result of Comparative Example 3,
Those containing the organic siloxane C have a remarkable decrease in transparency and are opaque. Furthermore, as is clear from the evaluation results of Comparative Example 4, C ₄ F ₉ SO ₃ exceeds the upper limit of the present invention.
When K is contained, not only is the oxygen index not greatly improved, but also the transparency is remarkably reduced and the film becomes opaque.

[0035]

As described above, according to the present invention,
Flame retardant PC that is hard to drip even when burned and has high transparency
It becomes possible to provide a resin composition.

Claims (1)

(57) [Claims] 1. An aromatic polycarbonate, an alkali (earth) metal salt of perfluoroalkanesulfonic acid, and an organic siloxane having an alkoxy group, a vinyl group and a phenyl group as essential components. Parts of the alkali (earth) metal salt of perfluoroalkanesulfonic acid is 0.03
To 0.3 parts by weight, the ratio of the organosiloxane is 0.0
A flame-retardant polycarbonate resin composition characterized by being 5 to 2.0 parts by weight.