JPH11255969A - Colored flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored flame-retardant composition having a clear color, high flame retardance and heat resistance in molding, by making the composition include a polyolefin, an organic halogen-based flame-retardant and a specific inorganic pigment. SOLUTION: This composition includes (A) a polyolefin (e.g. propylene homopolymer or the like), (B) an organic halogen-based flame-retardant [e.g. bis(dibromopropyl ether)-tetrabromobisphenol A or the like] and (C) an inorganic compound having a spinel type structure [Bi-Mo-V-oxide (yellow), Zn-Fe-oxide (yellow) or the like]. The composition comprises 2-40 pts.wt. of the component B and 0.01-15 pts.wt. of the component C based on 100 pts.wt. of the component A. Preferably, the composition contains further (D) 0.5-20 pts.wt. of a flame- retardant auxiliary (antimony trioxide, antimony pentoxide or the like) based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a colored flame-retardant resin composition having both high flame retardancy and excellent heat resistance during molding.

[0002]

2. Description of the Related Art Polyolefins have been used in industrial parts, because of their excellent chemical, physical and electrical properties.
Widely used in the field of appliance parts.

[0003] On the other hand, polyolefins have the property of being easily ignited and flammable, so that they cannot be directly used for inconvenient applications if burned. Require various flame retardants.

[0004] In particular, polyolefins which are recently used for exterior parts including heating elements such as household / home electric appliances and sanitary articles have a high degree of flame retardancy, such as "V-0" and "V-0" according to the US UL standard. V-2 "has been required.

[0005] Generally, flame retardation of polyolefin can be achieved by blending various flame retardants.
As the flame retardant, decabromodiphenyl ether,
Brominated flame retardants typified by brominated bisphenol A derivatives and brominated bisphenol S derivatives are generally used.

[0006] Polyolefins are often colored, and in recent years, in particular, with the improvement of quality of life, demands for a wide variety of colors have been increasing widely.

In general, polyolefins are colored by blending various pigments, and inorganic pigments and organic pigments are generally used as pigments.

[0008]

However, when a polyolefin that has been flame-retarded with an organic halogen-based flame retardant as described above is colored with a pigment, various problems occur, and the color is particularly brightly colored. The case becomes remarkable.

For example, when coloring a flame-retarded polyolefin with an inorganic pigment, the inorganic pigment has a property of poor coloring power, so that it is necessary to blend it in a large amount. There was a problem of lowering.

On the other hand, when a flame-retarded polyolefin is colored with an organic pigment, the organic pigment and the flame retardant act to cause discoloration, in addition to the disadvantage that the organic pigment has poor heat resistance. Has a problem that the flame retardancy is also reduced.

Therefore, there is a need for colored polyolefins having both high flame retardancy and excellent heat resistance.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, it has been found that a resin composition in which an inorganic pigment having a specific structure is blended with a flame-retarded polyolefin has a sufficient coloring property. The present invention has been found to have excellent heat resistance at the time of molding without impairing the flame retardancy as well as to achieve the present invention.

That is, the present invention is a flame-retardant resin composition comprising a polyolefin, an organic halogen-based flame retardant and an inorganic pigment, wherein the inorganic pigment is an inorganic compound having a spinel structure. It is a colored flame-retardant resin composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin used in the present invention is not particularly limited, and ethylene, propylene,
Α-olefin homopolymers such as 1-butene, 1-pentene, 4-methyl-1-pentene and 1-hexene, random or block copolymers of the above α-olefins, and mixtures of these polymers, etc. Can be mentioned.

Further, the copolymer may contain a monomer other than α-olefin, for example, vinyl acetate, as a copolymer component, as long as the properties of the copolymer are not impaired.

Further, a polymer other than polyolefin, for example, polyamide, may be mixed in an amount of, for example, 20% by weight or less as long as the physical properties of the polymer are not impaired.

Among the above, propylene homopolymer,
Propylene-based polymers such as random or block copolymers of propylene and α-olefins other than propylene are preferred.

The organic halogen-based flame retardant used in the present invention is not particularly limited, and examples thereof include hexabromobenzene, pentabromobenzene, pentabromotoluene, tetrabromotoluene, tetrabromoxylene, and tribromoxylene. Brominated aromatic hydrocarbon compounds such as bromoxylene, tetrabromophenol, tetrabromoresorcinol, tribromopyrogallol, brominated biphenyl, brominated diphenyl ether, brominated diphenylthioether, and brominated naphthalene derivatives; hexachlorobenzene, pentachlorobenzene, Pentachlorotoluene, tetrachlorotoluene, tetrachloroxylene, trichloroxylene, pentachlorophenol, tetrachlororesorcin, trichloropyrogal, chlorinated diphenyl ether, chlorinated diphe Chlorinated aromatic hydrocarbon compounds such as ruthioether and chlorinated naphthalene derivatives; chlorinated aliphatic hydrocarbon compounds such as tetrachlorobromobutane, pentachloropentane, hexachlorohexane, pentachloroheptane, and chlorinated paraffin; brominated bisphenol A, chlorinated bisphenol A, ether of brominated bisphenol A and brominated aliphatic alcohol, halogenated bisphenol A derivative such as ether of chlorinated bisphenol A and chlorinated aliphatic alcohol, brominated bisphenol S, chlorinated bisphenol S, halogenated bisphenol S derivatives such as ether of brominated bisphenol S and brominated aliphatic alcohol, ether of chlorinated bisphenol S and chlorinated aliphatic alcohol; tris (dibromopropyl) cyanurate, bis ( Brominated alkyl cyanurates such as brompentyl) cyanurate; brominated alkyl isocyanurates such as tris (dibromopropyl) isocyanurate, bis (dibromopropyl) isocyanurate and tris (tetrabromopentyl) isocyanurate; tris (dichlor) Chlorinated alkyl cyanurates such as propyl) cyanurate, bis (dichloropropyl) cyanurate and tris (tetrachloropentyl) cyanurate; tris (dichloropropyl) isocyanurate, bis (dichloropropyl) isocyanurate, tris (tetra Chlorinated alkyl isocyanurates such as chlorpentyl) isocyanurate; tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, tris [2,2-bis (bromomethyl) propyl] Tris (brominated neopentyl) phosphate such as phosphate and tris (2-bromomethyl-2-methylpropyl) phosphate; and the like.

In particular, in the present invention, the flame retardant is a tetrabromobisphenol S-based flame retardant represented by the following formula and / or
Or, in the case of a tetrabromobisphenol A-based flame retardant, when an inorganic compound having a spinel structure is blended as an inorganic pigment, sufficient coloring properties can be obtained, and excellent flame retardancy can be obtained without impairing the flame retardancy. This is preferable because the effect having the combined heat resistance is remarkably exhibited.

[0020]

Embedded image

R in the formula is an alkyl group to which at least two bromine atoms of the same or different kind are bonded, and preferably has 2 to 20 carbon atoms, more preferably 2 to 5 carbon atoms. Further, the larger the number of bromine atoms to be bonded, the better the flame retardant effect, which is preferable.

Specific examples of the compound represented by the above general formula include bis (dibromopropyl ether) -tetrabromobisphenol A, bis (dibromoethyl ether) -tetrabromobisphenol A, and bis (dibromobutyl ether) -tetrabromobisphenol A , Bis (tribromobutyl ether) -tetrabromobisphenol A, bis (tetrabromobutyl ether) -tetrabromobisphenol A, etc., tetrabromobisphenol A derivatives, bis (dibromopropyl ether)
-Tetrabromobisphenol S, bis (dibromoethyl ether) -tetrabromobisphenol S, bis (dibromobutyl ether) -tetrabromobisphenol S, bis (tribromobutyl ether) -tetrabromobisphenol S, bis (tetrabromobutyl ether) -tetrabromo Examples thereof include tetrabromobisphenol S derivatives such as bisphenol S. In the present invention, these can be used alone or as a mixture.

The compounding amount of the organic halogen-based flame retardant may be a compound exhibiting flame retardancy, for example, 2 to 40 parts by weight with respect to 100 parts by weight of polyolefin.
Preferably it is 3 to 30 parts by weight. In particular, when V-0 in the high flame retardant category is required, 8 to 30 parts by weight is preferable. When the amount of the organic halogen-based flame retardant is less than 2 parts by weight, sufficient flame retardancy cannot be obtained. When the amount is more than 40 parts by weight, not only the flame retardancy is not further improved but also the moldability. , Not only decrease in impact resistance, increase in specific gravity, etc.
It is not preferable because stable kneading work is difficult.

Further, the flame retardant resin composition of the present invention may further contain a flame retardant auxiliary. Examples of the flame retardant aid include antimony compounds (for example, antimony trioxide,
Examples include antimony pentoxide, antimony trichloride, and the like, boron compounds (for example, zinc metaborate, zinc tetraborate, zinc borate, and the like), zirconium oxide, tin oxide, and molybdenum oxide. And antimony pentoxide are preferred. These flame retardants may be used alone, or two or more flame retardants may be used in combination.

The mixing ratio of these flame-retardant aids is not particularly limited, but may be 0.1 to 100 parts by weight of polyolefin.
5-20 parts by weight are preferred. By combining flame retardant aids,
Acting synergistically on the halogen-based flame retardant, the flame retardancy can be increased, and the blending amount of the halogen-based flame retardant can be reduced. Therefore, in the present invention, the use of a flame retardant aid is preferred.

In the present invention, in order to color while having high flame retardancy and heat resistance, which are the effects of the present invention,
It is necessary to use an inorganic compound having a spinel structure as an inorganic pigment.

As the inorganic compound having a spinel structure used in the present invention, those usable as pigments can be used without any limitation. For example, Co-Al oxide (blue), Co-Al-Cr oxide ( Blue), Fe-Cr oxide (brown), Mg-Co-Al oxide (blue), Mg-C
Inorganic compounds such as o-Sn oxide (blue), Co-Fe-Al oxide (brown), Mg-Co-Cr oxide (green), and Mg-Fe oxide (red) can be given. Among them, Bi-Mo-V-oxide (yellow), Zn-
Inorganic compounds such as Fe-oxide (yellow) are preferred.

The amount of the inorganic compound having a spinel structure may be appropriately determined depending on the required color. For example, 0.01 to 100 parts by weight of polyolefin may be used.
It may be selected from a range of 15 parts by weight, preferably from 0.02 to 10 parts by weight. The amount of the inorganic compound is 0.01
When the amount is less than the weight part, a sufficient color cannot be obtained, which is not preferable. On the other hand, when the amount is more than 15 parts by weight, it is not preferable because not only no more color is obtained but also the flame retardancy is lowered.

In the present invention, the effect of obtaining sufficient coloring properties and having excellent heat resistance at the time of molding without impairing the flame retardancy is because the flame retardant is a tetrabromobisphenol S-based flame retardant. This is particularly noticeable in the case of a flame retardant and / or a tetrabromobisphenol A-based flame retardant.

On the other hand, an inorganic compound having no spinel structure, for example, an inorganic compound having a rutile structure based on titanium dioxide such as barium-nickel-titanium oxide and nickel-antimony-titanium oxide and a metal oxide. In the case where a compound or an iron oxide-based inorganic compound such as red iron oxide is used as a pigment, not only a vivid color is not obtained but also a reverse color as compared with the case where an inorganic compound having a spinel structure is used as a pigment. In some cases, the flame retardancy is reduced, which is not preferable.

The colored flame-retardant resin composition of the present invention may further comprise, if necessary, a conventionally known antioxidant (a phenol compound, a phosphorus compound, etc.) in addition to the components described above, as long as the effects of the present invention are not impaired. , Sulfur compounds, etc.), weathering agents (benzophenone, salicylate, benzotriazole, hindered amine, etc.), metal deactivators, antistatic agents (anion, cation, amphoteric), nucleating agents (metal salt) Sorbitol), fillers (such as talc, calcium carbonate, barium sulfate, glass fiber, mica, and hydrotalcite), neutralizing agents, dispersants, and lubricants.

In preparing the colored flame-retardant resin composition of the present invention, there are no particular restrictions on the order in which the components are mixed, the method of mixing, and the like. Generally, a tumbler-type blender, a V-type blender, a Henschel mixer, a ribbon mixer, and the like are used. And in a conventional manner.

Thereafter, generally, it is pelletized once using a general extruder such as a single screw extruder, a twin screw extruder or a tandem extruder, and then molded. Further, molding may be performed directly by an injection molding machine or an extrusion molding machine without passing through pelletizing.

The colored flame-retardant resin composition of the present invention not only has sufficient coloring properties, but also has excellent heat resistance during molding without impairing the flame retardancy. , Refrigerators, dish dryers, rice cookers, ventilation fans, pencil sharpeners, air purifiers, air conditioners, televisions, telephones, microwave ovens, water purifiers and other household and household appliances, toilet bowls (toilet seats, toilet lids, casings), toiletries It can be suitably used for sanitary articles such as bathroom appliances.

The colored flame-retardant resin composition of the present invention can be applied to conventional molding methods without any limitation. Further, when used in the above-mentioned applications, for example, a method obtained by injection molding,
A sheet may be formed by extrusion molding, and a molded body may be obtained by a method of obtaining the sheet by secondary processing such as vacuum molding and press molding.

[0036]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The symbols shown in the examples and comparative examples are as follows.

1. Resin A: propylene homopolymer (MFR: 40 g / 10 mi)
n) B: ethylene-propylene block copolymer (MFR:
2. 10 g / 10 min, monomer unit based on ethylene
1 wt%) 2. Flame retardant C: Tetrabromobisphenol S-bis (2,3-dibromopropyl) ether D: Tetrabromobisphenol A-bis (2,3-dibromopropyl) ether Pigment E: Bi-Mo-V oxide (BASF spinel type inorganic compound: Yellow 184) F: Zn / Fe-oxide (BASF spinel type inorganic compound: Yellow 119) G: Irgasin yellow (Ciba Geigy's isoindolinone type) Organic compound: Yellow109) H: Chromophthal yellow (condensed azo organic compound manufactured by Ciba-Geigy: Yellow93) I: Titanium yellow (rutile type inorganic compound manufactured by Nippon Fellow: Yellow53) Examples and Comparative Examples of colored flame-retardant resin composition The preparation and test method were performed as follows.

(1) Pre-kneading As shown in Table 1, a flame retardant, a flame retardant auxiliary, a pigment and an antioxidant (tetrakis- [methylene-3- (3,5-di -Butyl-4-hydroxyphenyl) -propionate] methane: 0.1
Parts by weight, dilauryl thiopropionate: 0.2 parts by weight) and premixed with a Henschel mixer.

(2) Pelletization The above mixture was pelletized using a vented 50 mmφ extruder.

(3) Effect test (a) Combustion test Using the pelletized material, UL was performed by an injection molding machine.
After forming vertical combustion test specimens conforming to the 94 standard, UL
A vertical combustion test was performed in accordance with the 94 standard to determine the flammability category.

(A) Heat Resistance Confirmation Test Using a pelletized material, a color plate test piece was molded at 200, 220 ° C. by an injection molding machine, and the color plate test piece molded at 200 ° C. was used as a blank. The color difference (ΔE) from the test piece molded at 220 ° C. was measured with a Hunter-type colorimeter, and the heat resistance was evaluated on a three-point scale.

○ No discoloration (ΔE: 0 to 0.5) △ Some discoloration (ΔE: 0.5 to 1) × Discoloration (ΔE: 1 or more) (c) Coloration confirmation test Use of pelletized material After the color plate test piece was molded at 200 ° C. by an injection molding machine, the b value (a measure of yellowness) was measured by a Hunter-type colorimeter.

Example 1 100 parts by weight of a propylene homopolymer as a polyolefin, 10 parts by weight of tetrabromobisphenol S-bis (2,3-dibromopropyl) ether as a flame retardant,
3 parts by weight of antimony trioxide as a flame retardant aid and 0.2 parts by weight of an inorganic compound having a spinel structure as a pigment were mixed and pelletized using a single screw extruder. The flammability, heat resistance and colorability of the pelletized material were evaluated and are shown in Table 1.

Examples 2 to 5, Comparative Examples 1 and 2 Types of polyolefin, flame retardant, flame retardant aid and pigment
The same operation as in Example 1 was performed except that the amount was changed to that shown in Table 1. The flammability, heat resistance and colorability of the pelletized material were evaluated and are shown in Table 1.

In order to confirm the effect of the present invention, the compounding amount of the flame retardant was adjusted so that the flame-retardant category when the pigment was not compounded was the same, and the compounding amount of the pigment was the same color. (B value was the same).

[0046]

[Table 1]

Examples 6 to 8, Comparative Examples 3 to 11 Types of polyolefin, flame retardant, flame retardant aid and pigment
The same operation as in Example 1 was performed except that the amount was changed to that shown in Table 2. The flammability, heat resistance and colorability of the pelletized material were evaluated and are shown in Table 2.

In order to confirm the effect of the present invention, the compounding amount of the flame retardant was adjusted so that the flame-retardant classification when no pigment was compounded was the same, and the compounding amount of the pigment was the same color. (B value was the same).

[0049]

[Table 2]

Examples 9 to 12, Comparative Examples 12 to 14 Types of polyolefin, flame retardant, flame retardant aid and pigment
The same operation as in Example 1 was performed except that the amount was changed to that shown in Table 3. The flammability, heat resistance and colorability of the pelletized material were evaluated and are shown in Table 3.

In order to confirm the effect of the present invention, the compounding amount of the flame retardant was adjusted so that the flame-retardant category when the pigment was not compounded was the same, and the compounding amount of the pigment was the same color. (B value was the same).

[0052]

[Table 3]

[0053]

As described in detail above, the colored flame-retardant resin composition of the present invention is characterized in that the inorganic compound having a spinel structure used has sufficient coloring performance, and that an organic halogen-based flame retardant is used. Because of its small interaction with, it has both high flame retardancy and high heat resistance during molding with vivid colors that have been considered difficult in the past. In addition, by using an inorganic compound having a spinel structure as a pigment, it is possible to solve the problems such as discoloration and a decrease in flame retardancy that occurred when a flame retardant polyolefin was colored in a vivid color with an organic pigment. Can be.

Therefore, the colored flame-retardant resin composition of the present invention is a useful material for home appliances, sanitary products and the like that require various colors.

Claims (1)

[Claims] 1. A flame-retardant resin composition comprising a polyolefin, an organic halogen-based flame retardant and an inorganic pigment, wherein the inorganic pigment is an inorganic compound having a spinel structure. Resin composition.