JPS58187450A - Resin composition - Google Patents

Abstract

PURPOSE:A flame-retardant resin composition having improved mechanical properties and thermal stability, obtained by blending a polycarbonate with an organic halogen compound and antimony trioxide treated with an alkoxysilane. CONSTITUTION:(A) 100pts.wt. polycarbonate, preferably 4,4,-dioxydiarylalkane- based polycarbonate having 20,000-40,000 average molecular weight is blended with (B) 0.1-20pts.wt., preferably 1-15pts.wt. calculated as an amount of halogen element of organic halogen compound such as hexabromobenzene, terachlorobisphenol A, etc. and (C) 0.1-20pts.wt., preferably 1-15pts.wt. calculated as amount of Sb element of antimony trioxide treated with an aloxysilane. The treatment of antimony trioxide blended as an auxiliary for flame retardance with the alkoxysilane will suppress the foaming during melting under heating, and reduces drop in physical properties without damaging appearance of a molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION In addition to the polycarbonate composition of the present invention, Fumensha has developed a polycarbonate composition that has excellent mechanical properties and thermal properties.

Holy carp is covered with mechanical properties and thermal properties.
-1', the molded product can be used in a wide range of applications.
However, recently, from the standpoint of saving resources, miniaturization and #metalization are progressing, and the demand for #solubilization is also becoming stronger.

Conventionally, it has been known to add a halogen compound as a flame retardant to make polycarbonate flame retardant, but the flame retardance of a thin molded product having a thickness of less than 1/16' was not sufficient.

- For flame retardation of polystyrene, polyglopylene, polybutylene terephthalate, etc., flame retardant aids such as antimony trioxide are added to halogen compound threads.
! It is known that when used in combination with agent I, a superior combustion effect can be obtained with a small amount compared to K.

However, when a composition containing polycarbonate and antimony trioxide as a flame retardant additive is heated and melted, it foams significantly, which not only impairs the appearance of the molded product but also causes a significant decrease in strength12, making it practically unusable. There was a drawback.

The inventors of the present invention have conducted intensive studies to solve the problem of flame retardation of polycarbonate, and as a result, they have developed antimony trioxide with a specific silane-based compound and used it as a retardant auxiliary agent. As the formula σ
) The fact that the light N is suppressed and the physical property low toe is small is ν
This is what led to the present invention.

1 rope b 1 piece) T, bright (included) polycarbonate not included) 100
J8! Kireroku Sanoxide Andemon Kai Anti-77
The present invention relates to a flank composition containing 1 to 20 parts by weight of C cord and L7 and U for sex characteristics.

The polycarbonate component used in the present invention is a thermoplastic polycarbonate having a level represented by the following general formula.

Preferred heat 1'iJ plastic polycarbonate is 4.4'
-dioxy, diallylalkane-based polycarbonates, such as bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ethane, 2.2-(4-
Hydroquinphenyl)prono(n, bis(4-hydroxy-3,5-dichlorophenyl)methane, 2,2-(4
-Hydroxy-a,S-dimethylphenyl)furopane, bis(4-hydroxyphenyl)phenylmethane, a,4'-cy*xydi-2-enyl alkane and phosgene or diphenyl carbonate. Note that the average molecule th of the polycarbonate used here is preferably about 20,000 to 40,000.

In the present invention, the organic compound used as the component (-) has a salt in the molecule! It has a bromine atom or a bromine atom and acts as a flame retardant for polycarbonate, and includes known organic compounds that are commonly used as flame retardants.

Such compounds include, for example, hexabromobenzene,
Hexachlorobenzene, pentapro7-toluene, bentacr1-mouth toluene, pentabromophenol, pentachlorophenol, hexypromodiphenyl decabromopyphenyl.

Tetrabromobutane, hexabromo7croto3decano,
Park mouth pentacyclotecan, tecaprosulfate; ether, octabromodiphenyl ether, hexafuromodiphenyl ether, ethylene bis(nato-2-pyromontalimide), tetrachlorobisphenol A,
Low molecular weight 4idkno1 of tetrabromobisphenol A
IX reactions between brominated polycarbonates (e.g. polycarbonates produced from brominated bisphenol A and 171i polycarbonate oligomers), brominated epoxy compounds (e.g. brominated bisphenol A and 1-pichlorohydride), Jepoxy compounds produced in this way, monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin), polychlorostyrene, brominated polystyrene, poly(diglomophenile/oxide), dechlorane plus (tetrachlorocyclopentadiene) It is also possible to use halogenated polymers and oligomers, such as 2 moles of cyclooctadiene and 1 mole of cyclooctadiene, or mixtures thereof.

These sonic halogen compounds have 0 per 100 parts by weight of polycarbonate as halogen source JK 凰.
．． 1 to aoi @ wrinkle part, preferably 1 to 15 electronic book part. If the amount is less than 0.1 part by weight, the flammability will not be sufficient, and if it exceeds 30 parts by weight, the physical properties of the composition will be markedly deteriorated, which is not preferable.

The antimony trichloride treated with alkoxy-7 silane used as component 1C) in the present invention has the effect of acting as a combustion aid that promotes the combustion properties of the above-mentioned organic halogen compound.

Antimony trioxide can be obtained, for example, by boiling antimony oxychloride, which is naturally occurring as annite, Valentine acupuncture, or a hydrolysis product of antimony chloride, with a 1ffF sodium solution.

Such antimony trioxide is generally used in VC as a viscosity additive for resins when used in combination with organic compounds, but as mentioned above, when used as 411 resin for polycarbonate, it foams when heated and melted. This results in poor appearance and reduced mechanical strength of the molded product.

However, if the above-mentioned antimony trioxide tube treated with the general formula % formula % (4 te, jt salable) is used as a combustion aid 7, foaming of polycarbonate can be considerably suppressed. A molded product with both appearance and strength that meets practical requirements can be obtained.

The alkoxysilanes mentioned above are preferred if
f, for example, methyltrimethoxysilane, methyltriethoxysilane, methertriisogropoxysilane, methyltributoxysilane, methylhatake...-octyloxysilane, methyltriphenoxysilane, phenyltrimethΦdisilane.

Phenyltriethoxysilane, vinyltriethoxysilane/vinyltritoxysilane, tetra2-ethylhexyl silicate, tetranolin silicate, tetratritenrus silicate.

γ-Gly7doxypropyltrimethoxysilane.

Examples include p-C3,4-evoquinchlorohexyl)ethyltrimethoxy7rane.

(2) Treatment of antimony trioxide with alkoxysilane can be carried out by bringing antimony trioxide and alkoxysilane 1 into contact with each other in the presence of Tsufu water and drying.
Put antimony trioxide in a mold blender, stir it, and treat it with 1 part of 0.1-2% Alcoquine 7-Ran water [or 1 water-organic solvent solution] while spraying with air or Vegas, and then dry it. Method: After dispersing antimony trioxide in water or an organic solvent to form a slurry, add a water bath solution of alkoxysilane and/or 1 agent solution, stir, and then stand still, allowing antimony dioxide to settle and separate. Drying method: It can be carried out by soufflé treatment of antimony trioxide produced in a heating furnace with Alu I-1-Nran water bath sap and/or an organic solvent solution, but it is necessary to
The method 1c of Kokura et al. is not limited to this.

Antimony trioxide barrel treated with alkoxysilane
In addition, the amount of polycarbonate 10G11 is 0.1~
20 mf parts, preferably 1 to 15 mf parts. If this amount is less than 0.1 part by weight, the effect as a tumor combustion aid will not be fully expressed. In addition, if the burnt young rice is more than 1 part of 20 parts, not only is the young rice almost saturated with 20 parts of L/JLI L, but also the properties of the resulting resin composition are If the value decreases, it is not a good trench.

Any method of compounding can be used to obtain the resin compositions of the present invention. Generally, it is preferable to disperse these ingredients more uniformly, and it is preferable to homogenize all or part of them at the same time or by mixing them in a mixer such as a blender, kneader, roll, extruder, etc. Some of the mixed ingredients may be mixed together or separately, e.g. by blending, kneading, rolling, etc.
Combine and mix the remaining ingredients in a mixer or press.
A method of mixing and homogenizing in an IT machine can be used.

Wax is also a common method, pre-triblended composition sounds! In this method, the mixture is melt-kneaded and homogenized in an extruder heated to 100 mL, extruded into a wire shape, and then cut into desired lengths and granulated. The composition thus prepared is usually sufficiently dried and kept in a dry state before being charged into a molding machine for molding.

Other methods include, for example, adding and mixing the same ingredients for producing polycarbonate.

The resin composition of the present invention may be blended with additives for the purpose of improving RC and other properties. For example, a fibrous material represented by glass fiber! Examples include 1IId + materials such as talc, mica, and glass peas, inorganic fillers in the form of powder, grains, or plate-like shapes, ultraviolet absorbers, 9 colorants, lubricants, and antistatic agents.

In addition, a small amount of other thermoplastic resins such as polyethylene, ABS resin, fluorocarbon resin, and other thermoplastic resins may be added.

The #I4 resin composition of the present invention can be easily molded by a conventional method using a general thermoplastic molding machine.The present invention will now be described in detail with reference to Examples. The 61 characteristics in Examples were measured by the following method.

(11 ratio blindness: ASTM D-7 (12K compliant (2
) % tensile strength: Conforms to ASTM D-+I38K (3) Flammability: Conforms to American Underwriters Laboratories standard Subject 94 ((JL-94)).

As a trial SS, length 5' x width 1/2' x thickness 1/16'
'It is used for molding by injection molding.

Reference example-A (alcoquinedinone-treated antimony dioxide-
Key of A! 1) Add 100 mtL of water to 10 mtL part of antimony trioxide, mix, and add menal tritoxysiphon (to m size) with adjusted strength and tightness. Drop the 25% acetone 4▲ lid part of 1 product name MTS-32), mix uniformly, and fc.

Thereafter, the mixture was transferred to a stainless steel vat and heated to 120°C.
Dry in the dryer set at .

Reference Example-B (Alkoxysilane-treated Annamon Pentoxide-B 1ii1 Notetraethyl/Licade (-Otona Kagaku Kogyo-1 Product Name 81-42) 100311 parts, 7X30 parts by weight, 151 m of acetic acid, 1 part of I and 55 ml of ethyl alcohol Using 231 parts of the mixed solution of Miyako, put it in a ribbon mixer and add 500 parts of triantimony oxide to Reference Example A in Sentence 11~.
A similar treatment was performed.

Examples 1-2 and Comparative Examples 1-5 1' Bisphenol AJf dried at 20°C for 5 hours
-Polycarbonate (Teijin Kasei ■l11!1IIi product name Panlite L-1250), @decabromodiphenyl ether (Mitsui Toatsu (14M, im product 6) as a flame agent)
Planelon DB-too) and the above-mentioned various antimony dioxides were added in the proportions shown in 44-1, and mixed uniformly using a ■ type blender.

The resulting mixture was transferred to a barrel Jlf28 using a 65mψ extruder.
Slenium 1° melted and mixed at 0°C and discharged from the die
was cooled and cut to obtain pellets for molding.

Then, the pellets were air-dried at 4120°C and 5:00 IMH1', and then a 5-ounce injection molding machine KwB test piece gold! ll Gold installed, cylinder temperature 80℃, 4
1 mold temperature 100℃, injection pressure 1000Kt/cd
A test specimen tube was molded under the following molding conditions: cooling time 20 seconds and total cycle time 35 seconds.

The appearance and specific gravity of the molded product thus obtained.

The tensile strength and flammability were measured. The results are shown in Table-1.

As is clear from the binding in Table 1, the combustion aid (trioxide)
antimony) was added to the system (Comparative Example 1.2).
However, in the systems (relative softness examples 3 and 4) in which 6 of the flame retardant aid (antimony dioxide untreated with alkoxysilane) was added, poor appearance and tF of specific gravity and tensile strength were observed.

On the other hand, in the embodiment of the present invention in which 3rH1 hyantemon treated with the alkoxylan of the present invention was added, the yield was 11M! Appearance 1 with scratches and no defects such as Examples 1 to 5
Ankylosis retention is tolerated.

However, 2, - trioxide treated with alkoxylan -//
rmong) When the amount added is large and the color becomes discolored (Comparative Example-5),
The appearance will be slightly worse and the specific gravity will be /J lower than the theoretical value.

Example 3 Bi;-triethoxysilane (Ten■S, *Product name V1
Using '5-E), antimony trioxide was treated in the same manner as in Example 1.

! #10 tightly adhered parts of polycarbonate obtained from tetrapromobisphenol carbonate (average degree of polymerization = 4) by refueling binding, 1 part of the above treated antimony trioxide 4x and 3 (l wt
% glass fiber reinforced polycarbonate) l OOill'
iJ′ club? After uniformly mixing with a V-type blender, Example 1~
Knead, extrude, and mold in the same manner as in 1. 1. At that time, no foaming phenomenon was observed in the molded product, and 3.

Claims (1)

[Claims] 100 parts of solid polycarbonate, (B) Kiku 4f
The amount of halogen element in i-halide d is 0.1-3
Resin whose sexual characteristics are 0.1 to 2ON1 01', and 01' to 2 ON1' as 0.0 to 0.01', and 0.1 to 2 ON1' as 0.01' to 0.1' to 0.1', and 0.1 to 2 ON1' as 0.01' to 0.1' to 0.1' to 0.01', and C which has been treated with (Cl'alcoquinine). Composition.