JPH0564663B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel stabilized polyester resin composition containing an inorganic filler, a metal, a metal oxide, or a pigment. [Prior art and its problems] Polyester resins such as polyethylene terephthalate and polytetramethylene terephthalate are
As plastics with relatively high heat resistance, fibers,
Although it is used as a film or as a molded product as a composition mainly containing glass fiber, UV rays and heating can cause oxidation of ester bonds.
Deterioration such as hydrolysis easily occurs, and this deterioration
The problem was that it was accelerated in the presence of inorganic fillers, metals, metal oxides, or pigments. Conventionally, methods of blending organic phosphoric acid or phosphite compounds or sterically hindered phenols have been known as methods for this stabilization. The present invention significantly prevents decomposition and oxidative deterioration of polyester resin even when additives such as inorganic fillers, metals, metal oxides, or pigments are added by blending compounds that are completely different from conventional methods. We have discovered a new stabilized polyester resin composition that can [Means for Solving the Problems] As a result of various studies on the use of the unique properties of cyanato groups in compounds having cyanato groups (-O-C≡N), the present invention has been developed using inorganic fillers, metals, or metal oxides. This work was completed based on the discovery that the heat deterioration properties of polyester resin compositions can be significantly improved by adding a cyanato group-containing compound to polyester resin compositions containing compounds or pigments. That is, the present invention provides a polyester resin composition containing an inorganic filler, a metal, a metal oxide, or a pigment, and a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule. This is a stabilized polyester resin composition made by mixing 0.1 to 10% by weight of The present invention will be explained below. The polyester resin of the present invention (hereinafter referred to as PES) usually uses terephthalic acid or dimethyl terephthalate as the main dicarboxylic acid component, and ethylene glycol, ethylene oxide, or 1,4-butanediol as the main diol component. Aromatic PESs such as condensed polyethylene terephthalate (hereinafter referred to as PET) and polytetramethylene terephthalate (hereinafter referred to as PBT) are blended with inorganic fillers, metals, metal oxides, or pigments as explained in the next section. and the polyester resin composition, polyolefins such as polyethylene, polypropylene, polyisobutylene, polyacetal resin, HIPS, AS,
Aromatic vinyl copolymers represented by ABS, MAS, MBS, MABS, etc., polyphenylene ether resins and mixtures of these and aromatic vinyl copolymers, polysulfone resins, polytetrachloroethylene, A resin composition containing coumaroindene resin, etc.; and plasticizers, flame retardants, ultraviolet absorbers, and additives other than those described in the next section.
This is a composition containing stabilizers and the like. The inorganic fillers that are blended in the PES of the present invention include calcium carbonate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide,
Talc, clay, mica, wollastonite, etc.; metals include powders, fibers, flakes, etc. of copper, iron, cobalt, nickel, chromium, manganese, aluminum, manganese, or alloys of these metals; Oxides include powders, fibers, flakes, etc. of copper oxide, iron oxide, antimony trioxide, and lead oxide, and pigments include organometallic compounds such as copper phthalocyanine (=phthalocyanine blue), yellow lead, and minerals. violet, carbon black,
They are metal oxides, metal composite oxides, etc. exemplified by iron oxide, ultramarine, cobalt blue, cobalt violet, titanium white, etc., and the amount of these additives added to PES is the usual amount,
In the case of inorganic fillers, it is used in an amount of about 5 to 70%, and in the case of pigments, it is used in an amount of about 0.01 to 5%. Incidentally, the PES 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 PES. 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 PES composition consisting of the above components are of the following general formula (1 ) General formula (1): R(OCN)m...(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 above cyanato group is bonded to the aromatic ring of the organic group). 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 PES 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 groups) per unit weight. )
It is more effective because there are more of them. If the amount added is less than 0.1%, the stabilizing effect is insufficient, and if it is used in excess of 10% by weight, it shows a remarkable effect in preventing deterioration, but other properties such as a reduction in the elongation of PES are impaired. So I don't like it.
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, -COOH, -NH ₂ , -
When it is necessary to add a compound having COOM, -SH, etc. (M=metal atom), it is preferable to avoid mixing the cyanate ester compound and these compounds in advance before adding them. The method of mixing the cyanate ester compound into the PES composition of the present invention may be any method as long as the cyanate ester compound is uniformly dispersed, and there are usually no particular limitations. For example, the above components are mixed in a blender or other means and made into pellets with an extruder, mixed in PES as a solution and dried, kneader,
A method in which the inorganic filler, metal, metal oxide or pigment of the present invention to be added and a cyanate ester compound are mixed in advance with a cyanate ester compound and used as is or extruded as pellets after being mixed with a Henschel mixer etc. There are also methods such as a method in which a semi-cured or cured film of a cyanate ester compound is formed on the surface of the additive component by heat treatment, and this is mixed with PES and extruded, and a master batch method in which a high concentration master batch is manufactured and mixed. This is suitable, and in the case of an extruder, the extrusion conditions for PES can be used as they are for mixing conditions. In other cases, it is sufficient to mix at room temperature or under heating, and the mixing time depends on the relationship with the temperature, but at a temperature of about 230 to 270°C, the effects of the present invention can be obtained even by mixing for about 2 to 3 hours. is maintained, so it is not particularly limited, but a method that causes less reaction of the cyanato groups in the cyanate ester compound is more preferable, and a shorter time is preferable under conditions that allow uniform mixing. [Example] The present invention will be explained below with reference to Examples. Note that the amounts added in Examples and the like are based on weight. Example 1 Fillers listed in Table 1 and 2,
2-bis(4-cyanatophenyl)propane (hereinafter referred to as BPA-CN) was added in the amount shown in Table 1, and kneaded in a kneader at a temperature of 265°C for 5 minutes. This mixture and test pieces were prepared from this mixture, and the physical properties were measured. The results are shown in Table 1 below. The physical properties were measured under the following conditions. MI: Melt index, unit g/10 min (temperature
260℃, load 2.16Kg, 10 minutes) (The smaller the MI value, the better the stability. Y _F A: Normal bending strength, unit Kg/mm ² Y _F D: Bending strength after treatment in oven at 150℃ for 116 hours, unit Kg/mm ² I _Z : Notched Izot impact value, unit Kg/cm/
cm In addition, test pieces were prepared by cutting out a 3 mm thick flat plate press-formed at 260°C. Example 2 Fillers listed in Table 2 and 1,4-dicyanatobenzene (hereinafter referred to as HQ-CN) were added to PBT (manufactured by Toray Industries, Inc., trade name: PBT1401),
After kneading in a kneader at a temperature of 240° C. for 5 minutes, this mixture was measured in the same manner as in Example 1, and the results are shown in Table 2 below. The MI measurement conditions were a temperature of 240°C, and the test pieces were press-formed at 240°C to a thickness of 3 mm.
The method was the same as in Example-1 except that the method was used to cut out from a flat plate. Example 3 A composition was produced and a test piece was prepared in the same manner as in Example 1, except that yellow lead, phthalocyanine blue, and HQ-CN were added to 100 parts of PET, and the bending strength was measured. The results are shown in Table 3 below.

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[Operation and effects of the invention]

As is clear from the above detailed description and Examples 1 to 3, the composition of the present invention has an effect of preventing thermal decomposition, an original color tone of the pigment seen in pigmented compositions, an effect of preventing thermal decomposition, etc. It can be seen that the composition significantly improves thermal deterioration and is extremely excellent in practical use.

Claims (1)

[Claims] 1 0.1 to 10 weight of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule is added to a polyester resin composition containing an inorganic filler, metal, metal oxide, or pigment. % stabilized polyester resin composition.