JPH0518350B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel stabilized polycarbonate resin composition containing an alkaline inorganic filler, a metal, a metal oxide, or a pigment. [Conventional technology and its problems] Polycarbonate resin is made of alcohol, salts,
It is stable against weak acids, but weak against alkalis.
Inorganic fillers such as calcium carbonate and calcium hydroxide, metals such as copper and iron and their oxides, pigments such as copper phthalocyanine, yellow lead, and gadmium were easily decomposed when heated and melted and mixed. The present invention is based on the discovery of a new stabilized polycarbonate resin composition that can significantly prevent the decomposition of polycarbonate resin even when these additives are added. [Means for Solving the Problems] As a result of various studies on the utilization of the unique properties of cyanato groups in compounds having cyanato groups (-O-C≡N), the present invention has developed an alkaline inorganic filler, metal or metal. This work was completed after discovering that the heat deterioration properties of polycarbonate resin compositions can be significantly improved by adding a compound having a cyanato group to polycarbonate resin compositions containing oxides or pigments. That is, the present invention provides an alkaline inorganic filler,
A polycarbonate resin composition containing metals, metal oxides, or pigments mixed with 0.1 to 10% by weight of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule. A stabilized polycarbonate resin composition. The present invention will be explained below. The polycarbonate resin of the present invention is a mixture of ordinary polycarbonate resins and various additives explained in the next section, and in particular aromatic polycarbonate resins made from bisphenol A, bisphenol A and tetrabromo bisphenol. A
In addition, these polycarbonate resins include aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene, polypropylene, and polyisobutylene, polyacetal resins, HIPS,
Aromatic vinyl copolymers represented by AS, ABS, MAS, MBS, MABS, etc., polyphenylene ether resins and mixtures of these and aromatic vinyl copolymers, polysulfone resins, A resin composition containing tetrachlorethylene, coumaroindene resin, etc.; and a composition containing plasticizers, flame retardants, ultraviolet absorbers, stabilizers, etc. other than the additives described in the next section. The alkaline inorganic fillers that are blended in the polycarbonate resin of the present invention include calcium carbonate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, talc, clay, etc., and the metals include copper, iron, etc. , cobalt, nickel, chromium, manganese, aluminum, manganese, or alloys of these metals, etc., and metal oxides include powders such as copper oxide, iron oxide, antimony dioxide, and lead oxide. , fibers, flakes, etc. Pigments include organic metal compounds such as copper phthalocyanine (=phthalocyanine blue), yellow lead, mineral violet, carbon black,
These include metal oxides and metal composite oxides, such as red oxide, ultramarine blue, cobalt blue, cobalt violet, and titanium white. The amount of these additives added to polycarbonate resin is the usual amount, which is about 5 to 70% for inorganic fillers and 0.01 to 5% for pigments.
used in moderate amounts. Incidentally, the polycarbonate resin composition of the present invention naturally includes compositions in which fillers other than the fillers exemplified above are used in combination with fillers that have been appropriately added to conventional polycarbonate resins. Suitable monofunctional or polyfunctional cyanate ester compounds containing one or more cyanato groups in the molecule of the present invention to be added as a stabilizer to the polycarbonate resin composition consisting of the above components are the following general formula ( 1): R(OCN) _n ...(1) (m in the formula is an integer of 1 or more and usually 5 or less, R ₂ is an aromatic organic group, and the cyanato group is an aromatic group of the organic group. (bonded to a ring). Specific examples include monocyanatobenzene, alkylcyanatobenzene such as P-tert-butylcyanatobenzene, monocyanatonaphthalene, 1,3- or 1,4-dicyanatobenzene, 1,3,5- Tricyanatobenzene, 1,3-,1,4-,1,6-,1,8
-,2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,
4'-dicyanatobiphenyl, bis(4-dicyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-
dichloro-4-cyanatophenyl)propane,
2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, These include tris(4-cyanatophenyl) phosphate and cyanic acid esters obtained by reacting novolak with cyanogen halides. In addition to these, Tokuko Shou 41-1928, Sho 43-
18468, 44-4791, 45-11712, 46-41112,
Cyanic acid esters described in JP-A No. 47-26853 and JP-A No. 51-63149 can also be used. In addition, molecules obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, organic metal salts, etc. It can be used as a prepolymer having a cyanato group therein, and it can also be used as a prepolymer with an amine. The amount of the cyanate ester compound of the present invention explained above in the polycarbonate resin is not particularly limited, but from the viewpoint of effectiveness, it is in the range of 0.1 to 10% by weight, and the monomer has more functional groups (-OCN) per unit weight. It is more effective because there are many groups). If the amount added is less than 0.1%, the stabilizing effect will be insufficient, and if it is used in excess of 10% by weight, it will have a remarkable effect on preventing deterioration, but other properties such as a decrease in the elongation of the polycarbonate resin will be impaired. This is not desirable because it can cause Furthermore, as explained above, since the effect of the present invention is due to the cyanato group, additives that react with this functional group such as -OH, -
If it is necessary to add a compound containing COOH, -NH ₂ , -COOM, -SH, etc. (M = metal atom), avoid mixing the cyanate ester compound and these compounds in advance. It is preferable to The method of mixing the cyanate ester compound into the polycarbonate resin composition of the present invention is not particularly limited as long as the cyanate ester compound is uniformly dispersed. and forming pellets with an extruder, mixing with polycarbonate resin as a solution and drying, mixing with a kneader, Henschel mixer, etc. and using as is or extruding to form pellets, and adding the inorganic filler of the present invention. , a method in which metals, metal oxides, or pigments and cyanate ester compounds are mixed in advance and a polycarbonate resin is mixed and extruded, and a masterbatch method in which a highly concentrated masterbatch is produced and mixed is also suitable. As for the mixing conditions, in the case of an extruder, the extrusion conditions for polycarbonate resin can be used as they are. In other cases, it is sufficient to mix at room temperature or under heating.
The mixing time depends on the relationship with the temperature, but is not particularly limited as the effect of the present invention is sufficiently maintained even with mixing for about 2 to 3 hours at a temperature of about 200 to 260°C. A method that causes less reaction of cyanato groups in the acid ester compound is more preferable, and a shorter time is preferable under conditions that allow uniform mixing. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts in Examples and the like are based on weight unless otherwise specified. Example 1 Fillers listed in Table 1 and 2,2-bis(4-cyanatophenyl)propane (hereinafter referred to as BPA-CN) were added to polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S2000). ) as the first
After adding the amount shown in the table and kneading in a kneader at a temperature of 250°C for 5 minutes, the melt index of this mixture was measured to evaluate stability. The results are shown in Table 1. The melt index was measured at a temperature of 250° C., a load of 2.16 kg, and a duration of 10 minutes, and was expressed in units of g/10 minutes. The smaller the value, the better the stability. The appearance of the resin flowed out was visually determined by melt index measurement and was indicated by the following code. ◎: Good gloss, 〇: No gloss Δ: Slightly foaming, ×: Foaming

[Table] Example 2 Polycarbonate resin similar to Example-1,
The pigments listed in Table 1 and 1,4-dicyanatobenzene (hereinafter referred to as HQ-CN) were added in the amounts listed in Table 2, and after kneading in a kneader at a temperature of 250°C for 5 minutes, the mixture was The stability was evaluated using the same measurements as in Example-1. The results are shown in Table 1.

[Table] Example 3 A composition prepared in the same manner as Test No. and in Example-1 and a composition obtained by using the same amount of talc in place of calcium carbonate were injection molded to form a 1.5 mm thick sample. Create a test piece and test it at normal temperature and at 130℃.
The bending strength was measured after heat treatment for 120 hours. The results are shown in Table 3.

[Operation and effects of the invention]

As is clear from the above detailed description and Examples 1 and 2, the composition of the present invention has excellent appearance such as surface gloss, the effect of preventing thermal decomposition, the original color tone of the pigment seen in pigmented compositions, and the heat resistance of the composition. It can be seen that the composition has significantly improved appearance and thermal deterioration, including the effect of preventing decomposition, and is an extremely excellent composition for practical use.

Claims (1)

[Claims] 1 Adding 0.1 to 10 of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule to a polycarbonate resin composition containing an alkaline inorganic filler, metal, metal oxide, or pigment. A stabilized polycarbonate resin composition formed by mixing % by weight.