JPS5996158A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent moldability and flame retardance and suppressed formation of flash during molding, by blending a specified halogen-contg. flame retarder and Sb2O3 with a thermoplastic polyester resin. CONSTITUTION:1-30pts.wt. (in terms of halogen atom) halogen-contg. flame retarder having an average MW of 1,000 or above, such as polytribromostyrene, 0.1-15pts.wt. (in terms of Sb) Sb2O3 having a simple mean particle diameter of 1-10mu and optionally, filler, nucleating agent, antioxidant, etc. are blended with 100pts.wt. thermoplastic polyester resin having an intrinsic viscosity of 0.40 or above as measured at a concn. of 1.2g/100ml in o-chloro-phenol at 35 deg.C, such as polytetramethylene terephthalate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition, and more particularly to a flame-retardant polyester composition with excellent moldability.

Typical thermoplastic polyesters include polyethylene terephthalate (hereinafter abbreviated as PET) and polyethylene terephthalate (hereinafter abbreviated as PBT), which are known as industrial molding materials and have excellent mechanical properties, It is widely used in electrical insulation parts, automobile parts, etc. due to its electrical properties, chemical resistance, heat resistance, etc.

In addition, demands for flame retardancy of molded products mainly for electrical insulation applications have become increasingly strict in recent years, and PET,
PBT is no exception, and we are responding to market demands by adding a large amount of flame retardant. Since such flame retardants are much more expensive than pace polymers, antimony trioxide is widely used as a flame retardant aid in order to obtain excellent flame retardant effects with a small amount of flame retardant.

By the way, although antimono trioxide, which is widely used as a combustion aid, is fine particles (usually 0.5μ or less), it aggregates during the mixing stage with thermoplastic polyester resin to form aggregated particles with a significantly large diameter. may occur, impairing surface appearance and mechanical properties. Regarding this point,
No. 2-32898 discloses decanol diphenyl ether.
chill (DBE) and/or decabromidiphenyl (D
BB) as a flame retardant.
If used in combination, foreign matter (agglomerated particles) with a particle size of 0.3 to several mm will be generated due to the aggregation of KSb20°, and the resulting product will have a significantly inferior surface appearance.''
I'-DBE and/or I) B The dispersed particle size of B is 3μ or less, preferably 1μ or less, and the dispersed particle size of sb, o is 3μ or less, preferably 2μ or less in terms of physical properties, especially in terms of tensile elongation at break. "Preferable." This dispersed particle size is an average particle size including aggregated particles.

In addition to the above-mentioned points, when antimony trioxide is added to thermoplastic polyester, it increases the melt fluidity of the thermoplastic polyester too much, for example, it flows into the slight gap in the special mold, resulting in molded products becoming flaky. Not only does deburring require a great deal of effort, but if the shape of the molded product is complex, deburring is virtually impossible and the method may not be practical. However,
No. 898 does not mention this problem or its solution at all.

As a result of intensive research aimed at improving the above-mentioned problems, the present inventors discovered that the generation of paris can be suppressed by using antimony trioxide with a specific particle size as a flame retardant aid. Reached.

That is, the present invention provides the following conditions: (4) Per 100 parts by weight of thermoplastic polyester resin, +B) halogen-based flame retardant with a molecular weight of 1000 or more - 1 to 30 parts by weight as the amount of halogen element and +C1 simple average particle size of 1 to 30 parts by weight The present invention relates to a resin composition characterized in that 0.1 to 15 parts by weight of antimony trioxide (10 μm) is blended as an antimony base.

In the thermoplastic polyester used as a carrier component in the present invention, the acid component is terephthalic acid, and the diol component is ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol.

The main target is polyesters consisting of at least one aliphatic diol such as neopentyl glycol.

Among these, preferred are polytetramethylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, etc., which have a fast crystallization rate.

Further, as the aromatic polyester, a part of the above-mentioned polyester may be substituted with a copolymer component, and examples of such copolymer component include isophthalic acid, phthalic acid; alkyl-substituted phthalate such as methyl terephthalic acid and methyl isophthalic acid. Acids; 2,6-naphthalene dicarboxylic acid, 2.
Naphthalene dicarboxylic acids such as 7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, etc.; 4,4
Diphenyldicarboxylic acids such as '-diphenyldicarboxylic acid, 3.4'-diphenyldicarboxylic acid, etc.; 4
, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid such as 4'-diphenoxyethanedicarboxylic acid, succinic acid.

Aliphatic or alicyclic dicarboxylic acids such as adipic acid, sepatic acid, azelaic acid, decanedicarboxylic acid, and cyclohexanedicarboxylic acids; alicyclic diols such as 1,4-cyclohexane dimetatool; dihydroxybenzene such as hydroquinone, resorcinol, etc. Q, 292-bis(4-hydroxyphenyl)-propane, 2.2-
Aromatic diols such as bisphenols such as bis(4-hydroxyphenyl)-sulfone, ether diols obtained from bisphenols and glycols such as two-handed range glycol; ε-oxycaproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid Examples include oxycarboxylic acids such as.

Further, an acid or glycerin having the ability to form a trifunctional or tetrafunctional ester such as a branching component such as tricarballylic acid, trimesic acid, trimellitic acid, etc. in the above-mentioned aromatic polyester.

An alcohol having a trifunctional or tetrafunctional ester-forming ability such as trimethylolpropane, pentaerythritol, etc. is mixed with at least 1.0 mol, preferably at least 0.5 mol, and more preferably at least 0.3 mol. The pages may be aligned.

The above-mentioned aromatic polyester used in the present invention preferably has an intrinsic viscosity of 0.40 or more, more preferably 0.45 or more. Here, the limiting viscosity is a value measured at a concentration of 1.21/100ml in orthochlorophenol at 35°C. The above-mentioned aromatic polyester can be produced by a conventional production method, such as a melt polycondensation reaction or a method combining this with a solid phase polymerization reaction. For example, to explain an example of producing polyethylene terephthalate, terephthalic acid or its ester-forming derivative (for example, lower alkyl ester such as dimethyl ester, monomethyl ester, etc.) and ethylene glyfur or its ester-forming derivative are combined in the presence of a catalyst. Polyethylene terephthalate can be produced by a method of causing a heating reaction and then polymerizing the obtained glycol ester of terephthalic acid to a predetermined degree of polymerization in the presence of a catalyst.

In the present invention, the halogenated flame retardant used as component [F]) has an average molecular weight of 1000 or more, such as halogenated polycarbonate oligomers (for example, polycarbonate oligomers produced using brominated bisphenol A as a raw material), halogenated Epoxy compounds (e.g., oligomeric epoxy compounds produced from brominated bisphenol A), 10-genated polystyrene (
Examples include polytribromostyrene, polypentabromostyrene), polydibromophenylene oxide, and the like.

With a molecular weight of 1000 or more, rogen-based surfactants do not bleed out onto the surface of the molded product, and do not bleed out onto the surface of the molded product.
Problems such as poor appearance, poor adhesion, and poor contact that occur with halogen-based flame retardants do not occur.

The amount of the halogen-based flame retardant used as the component (2) is 1 to 30 parts per 100 parts of thermoplastic polyester resin as the amount of halogen element.

If the amount of the halogen-based flame retardant is less than 1 part of the halogen element, no flame retardant effect will be observed, and if the amount of the halogen element is more than 30:ii parts, the mechanical strength will decrease, which is preferable. do not have.

Antiseptane dioxide used as a tel component in the present invention is ammonium dioxide having a simple average particle size of 1 to 10 μm. Preferably 1.2-8μ, more preferably 3-8μ
It has an average particle size of 7.5μ. Simple average particle size is 1μ
Smaller particles are undesirable because they tend to generate more paris. Such antimony dioxide can be produced by a generally known manufacturing method,
For example, a method of manufacturing by boiling ammonium oxychloride, which occurs naturally as balanite and valentinite, or a hydrolysis product of ammonium chloride, with an IJum solution;
Alternatively, among those manufactured by air oxidation of metal or antimony, those having the above-mentioned simple average particle size may be used.

(The amount of antimony trioxide used as the C1 component is
A suitable amount of antimony element is 0.1 to 15 parts by weight per 100 parts by weight of the thermal iJ string injection polyester resin. If the amount of antimony element is less than 0.1 part by weight, the effect of the flame retardant aid will hardly be observed, and if the amount of antimony element is more than 15 parts by weight, the physical properties such as mechanical strength will deteriorate significantly, making it practically impractical. Resistant to moths.

Various additives can be added to the resin composition of the present invention for the purpose of further improving other properties. 6 like this
1≦Additives include photonic agents such as glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, calcium sulfate fibers, steel fibers, ceramic fibers, boron whiskers, and other y-opening fibrous materials: Examples include inorganic fillers in the form of powder, single grain, or plate, such as silica, talc, calcium carbonate, glass peas, glass flakes, clay, and wollastonite.

These fillers are usually used as reinforcing material 1 surface modifiers,
Alternatively, it is blended for the purpose of modifying electrical, thermal, and other properties, but among these fillers, especially when glass fiber is used, it not only functions as a filler for reinforcing sleeves, but also acts as a nucleating agent as described below. Combined with its crystallization promoting effect, it exhibits excellent heat resistance and deformation stability.

Glass fibers that can be used for this purpose are not particularly limited as long as they are generally used for reinforcing resins. For example, long-fiber type (glass roving) and short-fiber chopped strands.

You can choose from milled fiber, etc. Glass fibers can also be used with sizing agents (e.g. polyvinyl acetate,
It may be treated with a polyester sizing agent, etc.), a coupling agent (for example, a silane compound, a borane compound, etc.), or other surface treatment agent. Furthermore, it may be covered with a resin such as a thermosetting resin or a thermosetting resin. Usually, long fiber type glass fibers are used by being cut into a desired length before or after blending with a resin, and this usage mode is also suitable for M in the present invention.

Furthermore, a known compound commonly used as a crystal nucleating agent can be added to promote crystallization of thermoplastic polyester resin. Examples of these nucleating agents include talc/titanium dioxide, benzoates, metal stearates, sodium mono- or polycarphonic acids, lithium salts, α-olefins and α,β-unsaturated carboxylic acids. An ionic copolymer consisting of a salt and the like can be exemplified.

Furthermore, for the purpose of improving heat resistance, antioxidants such as hindered phenol compounds, sulfur compounds, or heat stabilizers, such as phosphorus compounds such as trinochlorite phosphate, triphenyl phosphate, triphenyl phosphite, etc. can also be added.

Further, for the purpose of improving melt viscosity stability, hydrolysis resistance, etc., an epoxy compound may be added to each layer. Examples of epoxy compounds include bisphenol A-type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin, novolac-type epoxy compounds obtained from epichlorohydrin and aliphatic glycidyl ether novolac resins made by reacting various glyfurs or glycerol with evichlorohydrin, Alicyclic compound type epoxy compounds obtained from alicyclic compounds are preferred, and particularly preferred epoxy compounds include bisphenol A type epoxy compounds and diglycidyl ether of low molecular weight polyethylene glycol. Examples of other additives include ultraviolet absorbers, antioxidants, colorants, l'# agents, antistatic agents, and blowing agents.

In addition, in small proportions, other thermoplastic resins, such as sterol resins, acrylic resins, polypropylene, fluororesins, polyamide resins, polycarbonate resins, polysulfone, etc.; thermosetting resins, such as phenolic resins, melamine resins, Unsaturated polyester resins, silicone resins, etc., as well as soft thermoplastic resins, such as ethiyy-
(On vinyl copolymers, polyester elastomers, etc. may also be added.

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 there are various methods and methods for homogenizing all or part of them simultaneously or separately using a mixer such as a blender, kneader, roll, extruder, etc. A method can be used in which a part of the components are mixed simultaneously or separately, for example, using a slurender, kneader, roll, extruder, etc., and then the remaining components are mixed using these mixers or extruders to homogenize. .

The most common method is to homogenize the pre-triblended composition by melt-blending it in a heated extruder.
This is a method of extruding it into a wire shape, then cutting it to a desired length and granulating it. The resin composition thus produced is usually kept in a sufficiently dry state before being put into a molding machine hopper and subjected to molding. Further, as another method, for example, other components are added during the production of the thermoplastic polyester resin, before the polycondensation, after the polycondensation, or during the polycondensation.

One method is to mix them. In particular, when glass fiber is used as a filler, it is necessary to prevent it from shattering as much as possible during kneading.
In addition, for the purpose of improving workability during composition production, tri-blending may be performed without melting and mixing together with other components in an extruder. A composition prepared by mixing thermoplastic polyester resin granules with a predetermined amount of glass chopped strands or a pre-adjusted glass fiber-rich thermal VJ plastic resin can also be charged into a molding machine hopper and subjected to molding.

The resin composition of the present invention can be easily molded by a conventional method using a general thermoplastic resin molding machine. Moreover, the generation of flakes during molding is suppressed, and complex molded products can be easily obtained.

The present invention will be described in detail below with reference to Examples.

Various properties in the examples were measured by the following methods.

The particle size distribution of the antimony dioxide sample was measured using a particle size distribution measuring device (Shimadzu particle size distribution automatic measuring device R5-1000; manufactured by Shimadzu Corporation) using a specific gravity bottle method using a liquid phase sedimentation method. The measurement sample was added to 3 o o cc of water.
, o s % of sodium ligninsulfonate was dissolved, and 7.35 p of antimony trioxide was added thereto and uniformly dispersed.

From this distribution curve, the simple average particle size was determined to be the cumulative particle size of 50 weight percent.

(2) Paris index: width 20mm, thickness 0.5ml1llO in the same cavity
Injection pressure sookg/ffl was applied to an evaluation mold having flow path A and flow path B with a width of 26 mm and a thickness of 0.05 mm.

The flow length ratio when the resin was flowed at an injection speed of 507/sec was defined by the formula below, and was taken as the Paris index.

Paris index (F, I) = flow length of wall thickness 0.05 mm (c
IrL) ÷ wall thickness o, flow length of smm part ← 蒲) x 100 (
3) Static strength tensile test: Based on ASTM D-638.

Examples 1 to 5 and Comparative Examples 1 to 3 PET with an intrinsic viscosity of 0.71 dried at 130°C for 5 hours
Glass chopped strand with a length of 3 mm on the tip,
The thinning agent was added in the amount ratio shown in Table 1, and mixed uniformly using a V-type blender.

The resulting mixture was heated to a barrel temperature of 2 using an extruder with a diameter of 651 nm.
The mixture was melted and mixed at 70° C., and the thread discharged from the die was cooled and cut to obtain pellets for molding.

Next, this pellet was dried with hot air at 130°C for 5 hours, and then a Paris index measuring mold was attached to a 5-ounce injection molding machine, and the cylinder temperature was 270°C, the mold temperature was 70°C, and the injection pressure was sookg/di.

The entire cycle was 30 seconds.

The flow length of the o, smm thick part and the flow length of the o, osmm thick part of the thus obtained molded product were measured and the Paris index was determined. Table 1 also shows the results of measuring the rate of occurrence of 741 when molded.

From Table 1, the simple average particle size of antammon trioxide is 0.7μ.
It can be seen that as the value becomes smaller, the Paris index increases rapidly, whereas when the value is larger than 1.2μ, especially 4μ, the Paris index is stable and becomes a region where almost no Paris occurs.

Examples 6 to B and Comparative Example 4 After adding flame retardants and the like in the proportions shown in Table 2 to PBT with an intrinsic viscosity of 1 and 05 dried at 120°C for 5 hours and mixing uniformly, the mixture was extruded into a barrel using a 65 mmφ extruder. The mixture was melted and mixed at a temperature of 250° C., and the thread discharged from the die was cooled and cut to obtain a pellet for molding. Next, this beret is 12
After drying with hot air at 0℃ for 5 hours, a Paris index measurement Venus was attached to a 5-ounce injection molding machine, and the cylinder temperature was 240℃.
℃, a mold temperature of 70°C, an injection pressure of sookg/i, and a total cycle of 30 seconds, and the Paris index was determined in the same manner as in Example 1. In addition, tensile test pieces were molded under similar molding conditions and evaluated.

These results are shown in Table 2.

Table 2 shows that PBT has the same pari generation situation as PET, and shows a high yziZ'J index when the simple average particle size of antimony trioxide is 0.5 μ; It can be seen that the unexpected result that the tensile elongation at break due to the force ζ is large is obtained.

Table 2

Claims (1)

[Scope of Claims] (2) Heat 5'f per 100 parts by weight of lidding polyester resin, [F]) halogen-based flame retardant with a molecular weight of 1000 or more as a halogen element amount of 1 to 30fi total and fc) simple average A resin composition comprising 0.1 to 15 parts of antimony trioxide having a particle size of 1 to 10 microns as an elemental amount of antimony.